Carboalkoxy alkyl norbornanes, organoleptic uses thereof and process for preparing same

ABSTRACT

Described is a process for augmenting or enhancing the aroma or taste of a foodstuff or chewing gum comprising the step of adding to a foodstuff or chewing gum an aroma augmenting or enhancing quantity of a product comprising a major proportion of compounds defined according to the structure: ##STR1##

This is a divisional of application Ser. No. 206,466, filed 11/13/80 nowU.S. Pat. No. 4,312,888, which in turn, is a continuation-in-part ofapplication for U.S. Letters Patent, Ser. No. 133,870 filed 3/25/80 nowU.S. Pat. No. 4,319,036.

BACKGROUND OF THE INVENTION

The present invention relates to carboalkoxy alkyl norbornanes havingthe generic formula: ##STR2## wherein the dashed line represents eithera carbon-carbon single bond or a carbon-carbon double bond; R₁, R₂, R₃,R₄, R₆ and R₇ represents hydrogen or methyl; with the proviso that oneof R₁, R₂, R₆ and R₇ is methyl and each of the other of R₁, R₂, R₆ andR₇ is hydrogen; and with the further proviso that R₃ and R₄ are not bothmethyl, produced by the novel process of our invention, and to novelcompositions using one or more of such norbornane derivatives to alter,modify or enhance the flavor and/or aroma of consumable materials orimpart flavor and/or aroma to consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors andfragrances to (or in) various consumable materials. These substances areused to diminish the use of natural material, some of which may be inshort supply, and to provide more uniform properties in the finishedproduct.

Fruity, burnt fruit-like, raspberry, sweet, seedy, berry-like, redberry-like, blueberry-like, spicy, black pepper-like, herbaceous,clove-like, vermouth-like, strawberry-like, wild strawberry-like,camphoraceous and balsamic aromas with fruity burnt fruit-like,raspberry, seedy, sweet, berry-like, red berry-like, blueberry-like,spicy, black pepper-like, herbaceous, clove-like, vermouth-like,strawberry-like, wild strawberry-like, camphoraceous, balsamic andbitter tastes are particularly desirable for many uses in foodstuffflavors, chewing gum flavors, toothpaste flavors and medicinal productflavors.

Spicy, cooling, clove-like, cinnamon bark-like, sweet, fruity,berry-like, juicyfruit, woody, piney, blueberry, banana, green,herbaceous, strawberry-like and dill aroma and taste characteristicsboth prior to and on smoking in the mainstream and in the side stream.

Intense and pleasant fruity, strawberry-like, raspberry, Resedabody-like, banana-like, creamy, camphoraceous, herbaceous, sweet, spicy,woody, eucalyptol-like, rum/butterscotch-like, balsamic, green, minty,borneol-like and "medicinal" aromas with strong camphor, minty andcalamnus-like undertones are desirable in several types of perfumecompositions, perfumed articles and colognes.

Arctander, "Perfume and Flavor Chemicals", 1969, Volume I discloses theuse in perfume compositions and in foodstuff flavors of camphenecarbinyl acetate thus:

"1029: 2,2-Dimethyl-Delta-2-beta-norbornane-2-ethylacetate "CampheneCarbinyl acetate". ##STR3## Mild and sweet-woody odor with afloral-piney undertone. The commercial products are probably not welldefined single chemicals, and great variations in odor have beenobserved. This ester has been developed in line with the research onSandalwood type odors. The parent alcohol "Camphene carbinol" was onceconsidered useful as a Sandalwood type material, but is has found moreuse as a sweetening and enriching ingredient in sophisticated Pinefragrances. The title ester finds limited use in perfume compositions ofwoody character, Fougeres, Pine fragrances, etc. and it blends very wellwith the Cyclohexanol derivatives, Ionones, iso-Bornyl-acetate,Nitromusks, etc."

Mellor and Webb, J. Chem. Soc. Perkin Trans II, 1974 (I) 26-31 disclosesproduction of the compounds having the structures: ##STR4## togetherwith several other methyl substituted isomers thereof in admixture,according to the reaction: ##STR5## The Mellor and Webb article however,does not disclose the reaction to take place at low temperatures in thepressence of an alkyl aluminum halide or dialkyl aluminum halide wherebybut two isomers are produced in a controlled fashion in high yields thusyielding an organoleptically acceptable mixture of carboalkoxynorbornane derivatives.

Thus, nothing in the prior art indicates production for organolepticuses of compounds having the generic structure: ##STR6## wherein thedashed line represents a carbon-carbon single bond or a carbon-carbondouble bond and R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined above.

U.S. Pat. No. 4,143,074 discloses, generically, compounds which areesters and contain the norbornyl moiety having the structures: ##STR7##wherein either or both of R₁ or R₂ is hydrogen or lower alkyl, R₃ ishydrogen or lower alkyl and n is zero or 1 and in addition, the compoundhaving the structure: ##STR8## wherein R₆ is alkyl having from one up toeight carbon atoms.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 sets forth the GLC profile for the reaction product of Example Icontaining compounds having the structures: ##STR9##

FIG. 2A is the NMR spectrum for fraction 8 of the distillation productof the reaction product of Example I having the structure: ##STR10##

FIG. 2B represents the NMR spectrum for fraction 2 of the distillationproduct of the reaction product of Example I having the structure:##STR11##

FIG. 3A represents the infrared spectrum for fraction 8 of thedistillation product of the reaction product of Example I having thestructure: ##STR12##

FIG. 3B represents the infrared spectrum for fraction 2 of thedistillation product of the reaction product of Example I having thestructure: ##STR13##

FIG. 4 represents the mass spectrum for the reaction product of ExampleI containing compounds having the structures: ##STR14##

FIG. 5 represents the GLC profile for the reaction product of Example IIcontaining compounds having the structures: ##STR15##

FIG. 6A represents the NMR spectrum of peak 1 of the GLC profile of FIG.5 consisting essentially of the compound having the structure: ##STR16##

FIG. 6B represents the NMR spectrum for fraction 6 of the distillationproduct of the reaction product of Example II consisting essentially ofthe compound having the structure: ##STR17##

FIG. 7A represents the infrared spectrum for peak 1 of the GLC profileof FIG. 5 of the reaction product of Example II consisting essentiallyof the compound having the structure: ##STR18##

FIG. 7B represents the infrared spectrum for fraction 6 of thedistillation product of the reaction product of Example II having thestructure: ##STR19##

FIG. 8 represents the mass spectrum of the reaction product of ExampleII containing compounds having the structures: ##STR20##

FIG. 9 represents the GLC profile of the reaction product of Example IIIcontaining compounds having the structures: ##STR21##

FIG. 10A represents the NMR spectrum for fraction 10 of the distillationproduct of the reaction product of Example III containing the compoundhaving the structure: ##STR22##

FIG. 10B represents the NMR spectrum for fraction 6 of the distillationproduct of the reaction product of Example III containing the compoundhaving the structure: ##STR23##

FIG. 11A represents the infrared spectrum for fraction 10 of thedistillation product of the reaction product of Example III containingthe compound having the structure: ##STR24##

FIG. 11B represents the infrared spectrum for fraction 6 of thedistillation product of the reaction product of Example III containingthe compound having the structure: ##STR25##

FIG. 12 represents the mass spectrum for the reaction product of ExampleIII containing compounds having the structures: ##STR26##

FIG. 13 represents the GLC profile of the crude reaction product (washedbefore distilling) of Example IV containing the compounds having thestructures: ##STR27##

FIG. 14 represents the GLC profile for bulked fractions 7-12 inclusiveof the distillation product of the reaction product of Example IV(conditions: Carbowax column programmed at 80°-122° C. at 8° C. perminute).

FIG. 15A represents the NMR spectrum for the reaction product of ExampleIV containing the compound having the structure: ##STR28##

FIG. 15B represents the NMR spectrum for the reaction product of ExampleIV containing the compound having the structure: ##STR29##

FIG. 16A represents the infrared spectrum for the reaction product ofExample IV containing the compound having the structure: ##STR30##

FIG. 16B represents the infrared spectrum for the reaction product ofExample IV containing the compound having the structure: ##STR31##

FIG. 17 represents the mass spectrum for the reaction product of ExampleIV containing the compounds having the structures: ##STR32##

FIG. 18 represents the GLC profile for the reaction product of Example Vcontaining the compounds having the structures: ##STR33##

FIG. 19A represents the NMR spectrum for fraction 9 of the distillationproduct of the reaction product of Example V containing the compoundhaving the structure: ##STR34##

FIG. 19B represents the NMR spectrum for fraction 1 of the distillationproduct of the reaction product of Example V containing the compoundhaving the structure: ##STR35##

FIG. 20A represents the infrared spectrum for fraction 9 of thedistillation product of the reaction product of Example V containing thecompounds having the structure: ##STR36##

FIG. 20B represents the infrared spectrum for fraction 1 of thedistillation product of the reaction product of Example V containing thecompound having the structure: ##STR37##

FIG. 21 represents the mass spectrum for the reaction product of ExampleV containing the compounds having the structures: ##STR38##

FIG. 22 represents the GLC profile for the reaction product of ExampleVI containing the compounds having the structures: ##STR39##

FIG. 23A represents the NMR spectrum for fraction 14 of the distillationproduct of the reaction product of Example VI containing the compoundhaving the structure: ##STR40##

FIG. 23B represents the NMR spectrum for fraction 4 of the distillationproduct of the reaction product of Example VI containing the compoundhaving the structure: ##STR41##

FIG. 24A reresents the infrared spectrum for fraction 14 of thedistillation product of the reaction product of Example VI containingthe compound having the structure: ##STR42##

FIG. 24B represents the infrared spectrum for fraction 4 of thedistillation product of the reaction product of Example VI containingthe compound having the structure: ##STR43##

FIG. 25 represents the mass spectrum for the reaction product of ExampleVI containing the compounds having the structures: ##STR44##

FIG. 26 represents the GLC profile for the reaction product of ExampleVII containing the compounds having the structures: ##STR45##

FIG. 27 represents the NMR spectrum for the reaction product of ExampleVII containing a mixture of the compounds having the structures:##STR46##

FIG. 28 represents the infrared spectrum for the reaction product ofExample VII containing a mixture of the compounds having the structures:##STR47##

FIG. 29 represents the mass spectrum for the reaction product of ExampleVII containing a mixture of the compounds having the structures:##STR48## FIG. 30 sets forth the GLC profile for the reaction product ofExample VII -A (bulked fractions 3-5 after distillation) consisting ofthe compounds having the structures:

FIG. 31-A sets forth the NMR spectrum for fraction 1 of the distillationproduct of the reaction product of Example VII -A consisting of thecompound having the structure: ##STR49##

FIG. 31-A sets forth the the NMR spectrum for peak 2 of the GLC profileof the reaction product of Example VII -A consisting of the compoundhaving the structure: ##STR50##

FIG. 32-A sets forth the infrared spectrum for fraction 1 of thedistillation product of the reaction product of Example VII -Aconsisting of the compound having the structure: ##STR51##

FIG. 32-B sets forth the infrared spectrum for peak 2 of the GLC profileof the reaction product of Example VII -A consisting of the compoundhaving the structure: ##STR52##

FIG. 33-A sets forth the mass spectrum for fraction 1 of thedistillation product of the reaction product of Example VII -Aconsisting of the compound having the structure: ##STR53##

FIG. 33-B sets forth the mass spectrum for peak 2 of the GLC profile ofthe reaction product of Example VII -A consisting of the compound havingthe structure: ##STR54##

FIG. 34 is the GLC profile (conditions: carbowax programmed at 80°-220°C. at 8° C. per minute) of the reaction product of Example XXXIIcontaining the compounds having the structures: ##STR55##

FIG. 35-A is the NMR spectrum for Peak 1 of the GLC profile of FIG. 34containing the compound having the structure: ##STR56##

FIG. 35-B is the NMR spectrum for Peak 2 of the GLC profile of FIG. 34containing the compound having the structure: ##STR57##

FIG. 36-A is the infra-red spectrum for Peak 1 of the GLC profile ofFIG. 34 containing the compound having the structure: ##STR58##

FIG. 36-B is the infra-red spectrum for Peak 2 of the GLC profile ofFIG. 34 containing the compound having the structure: ##STR59##

FIG. 37 is the GLC profile for the reaction product of Example XXXIII(conditions: SE-30 column programmed at 80°-220° C. at 8° C. per minute)containing the compounds having the structures: ##STR60## (reactionproduct before distillation).

FIG. 38-A is the NMR spectrum for Fraction 1, Peak 1 of the distillationproduct of the reaction product of Example XXXIII containing thecompounds having the structures: ##STR61##

FIG. 38-B is the NMR spectrum for Fraction 8, Peak 2 of the distillationproduct of the reaction product of Example XXXIII containing thecompounds having the structures: ##STR62##

FIG. 39-A is the infra-red spectrum for Fraction 1, Peak 1 of thedistillation product of the reaction product of Example XXXIIIcontaining the compounds having the structures: ##STR63##

FIG. 39-B is the infra-red spectrum for Fraction 8, Peak 2 of thedistillation product of the reaction product of Example XXXIIIcontaining the compounds having the structures: ##STR64##

FIG. 40-A is the NMR spectrum for Fraction 2, Peak 1 of the distillationproduct of the reaction product of Example XXXIV containing thecompounds having the structures: ##STR65##

FIG. 40-B is the NMR spectrum for Fraction 10, Peak 2 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR66##

FIG. 41-A is the infra-red spectrum for Fraction 2, Peak 1 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR67##

FIG. 41-B is the infra-red spectrum for Fraction 10, Peak 2 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR68##

FIG. 42 is the GLC profile for the reaction product of Example XXXVcontaining the compounds having the structures: ##STR69##

FIG. 43-A is the NMR spectrum for Peak 1 of the GLC profile of FIG. 42of the reaction product of Example XXXV containing the compound havingthe structure: ##STR70##

FIG. 43-B is the NMR spectrum for Peak 2 of the GLC profile of FIG. 42for the reaction product of Example XXXV containing the compound havingthe structure: ##STR71## FIG. 44-A is the infra-red spectrum for Peak 1of the GLC profile of FIG. 42 of the reaction product of Example XXXVcontaining the compound having the structure:

FIG. 44-B is the infra-red spectrum for Peak 2 of the GLC profile ofFIG. 42 of the reaction product of Example XXXV containing the compoundhaving the structure: ##STR72##

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, medicinal product and toothpaste compositions and flavoringcompositions therefor having the fruity, burnt fruit, raspberry, seedy,sweet, berry-like, red berry-like, blueberry-like, spicy, blackpepper-like, herbaceous, clove-like, vermouth-like, strawberry-like,wild strawberry-like, camphoraceous and balsamic aroma characteristicsand flavor characteristics as well as bitter taste characteristics; aswell as novel smoking tabacco and smoking tobacco flavoring compositionshaving spicy, cooling, clove-like, cinnamon bark-like, sweet, fruity,berry-like, juicyfruit, woody, piney, blueberry, banana, green,herbaceous, strawberry-like and dill aroma and taste prior to and onsmoking in both the mainstream and the sidestream; as well as novelperfume compositions, colognes and perfumed articles (e.g., solid orliquid anionic, cationic, nonionic or zwitterionic detergents, fabricsofteners and dryer-added fabric softener articles) having intense andlong lasting fruity, banana, creamy, camphoraceous, strawberry-like,raspberry, reseda body-like, herbaceous, sweet, spicy, woody,eucalyptol-like, rum/butterscotch-like, balsamic, green, minty,borneol-like, and medicinal aromas with strong camphor, minty andcalamnus-like undertones may be provided by utilization of one or moreof the substituted norbornane derivatives having the generic structure:##STR73## wherein the dashed line represents either a carbon-carbonsingle bond or a carbon-carbon double bond and R₁, R₂, R₃, R₄, R₆ and R₇represent either hydrogen or methyl with the proviso that one of R₁, R₂,R₆ and R₇ is methyl and each of the other of R₁, R₂, R₆ and R₇ ishydrogen; and with the further proviso that R₃ and R₄ are not bothmethyl, in foodstuffs, chewing gums, toothpastes, medicinal products,perfume compositions, perfumed articles, colognes and smoking tobaccosas well as smoking tobacco substitutes.

Unless otherwise specified, representations herein are intended toindicate "cis" isomers, "trans" isomers, mixtures of "cis" and "trans"isomers and "endo" isomers and "exo" isomers with respect to thenorbornane ring moiety and dextro and levvortatory isomers as well asracemic mixtures of optical isomers of the norbornance derivatives ofour invention.

Thus, the generic structure: ##STR74## is intended to mean both "endo"and "exo" isomers having the structures: ##STR75##

The novel substituted norbornane derivatives of our invention useful asindicated supra may be produced by reacting a 1-methylcylopentadiene or2-methylcyclopentadiene having one of the structures: ##STR76## or amixture of these methylcyclopentadienes defined according to the genericstructure: ##STR77## with an alkyl acrylate derivative defined accordingto the generic structure: ##STR78## in the presence of a specific Lewisacid catalyst at relatively low temperatures (e.g., 0°-50° C.) or in theabsence of a catalyst at relatively high temperatures (e.g., 170°-250°C.).

When using the catalytic process of our invention, an isomer mix will beproduced which contains isomers in proportions and (in some cases)having structures different from the proportions and (in some cases)structures produced using the high temperature reaction of our invention(which reaction is carried out in the absence of catalyst).

The reactant having the structure: ##STR79## represents a "cis" isomeror a "trans" isomer or a mixture of "cis" and "trans" isomers. Thus, the"trans" isomer may be represented by the structure: ##STR80## and the"cis" isomer may be represented by the structure: ##STR81##

When performing the process for preparing compounds useful in thepractice of our invention where the use of a catalyst is required, thecatalyst for the reaction may be an alkyl aluminum dihalide or a dialkylaluminum halide for example RAlCl₂ or R₂ AlCl wherein R representsmethyl, ethyl or n-propyl or i-propyl. The preferred catalyst is ethylaluminum dichloride. Other Lewis acids such as aluminum trichloride,stannic chloride, zinc chloride, ferric chloride and titaniumtetrachloride have been attempted to be used but such attempts haveproved to be unsuccessful with minimal or no yields of product beingproduced. The temperature range of the reaction may vary from about 0°C. up to about 50° C. with ambient temperatures, from 20° up to 30° C.being preferred. The reaction pressure will not affect the yield butconveniently and economically, a reaction pressure of atmospheric ispreferred. Thus, the catalyst for the reaction may be defined accordingto the formula: R_(m) ' AlCl_(n) wherein R' is C₁ -C₃ alkyl and the sum,m+n, equals 3; with m being one or two and n being one to two.

The reaction mass resulting from the catalytic process is a mixture ofcompunds containing unsaturation in the norbornane moieties definedaccording to the generic structures: ##STR82##

When performing the reaction for preparing compounds useful in thepractice of our invention in the absence of catalysts (that is where nocatalyst is required), the reaction temperature is in the range of fromabout 170° C. up to about 250° C. with a temperature of 200° C. beingpreferred. When the reaction is carried out at such high temperatures,the reaction is carried out under pressures greater than atmospheric ina closed pressurized system. The pressure of reaction may vary fromabout 10 psig up to about 100 psig depending on the vapor pressure ofthe reaction mass and depending upon the temperature at which it isdesired to carry out the reaction. Thus, reaction pressures of between10 psig and 100 psig will not in and of themselves affect the yield ofproduct although too high a temperature of reaction will affect theyield of product in view of the higher degree of decomposition and toolow a reaction temperature will affect the yield of product in that thereaction will take an inordinately long period of time in order toachieve a given yield. Thus, it appears that the optimum reactiontemperature in the absence of catalyst is 200° C. Reaction temperaturesbelow 170° C. will not be high enough to effect the initiatingdecomposition of the dimethyl dicyclopentadiene starting material whichit is most practical to use as a precursor of the dimethyldicyclopentadiene.

The reaction mass resulting from the "thermal-non-catalytic" process isalso a mixture of compounds containing unsaturation in the norbornanemoiety defined according the the generic structures: ##STR83## whereinR₃, R₄ and R₅ are as defined above.

The above unsaturated compounds may be used "as is" for their individualorganoleptic properties or mixtures of compounds may be used "as is" fortheir organoleptic properties or the compounds individually or inadmixture may be further hydrogenated using hydrogen gas at superatmospheric pressures. When it is desired to use the compounds "as is"for their organoleptic properties, it is referable to refine thereaction mass as by fractional distillation or high pressure liquidchromatography thereby creating one or more products usable as set forthabove.

When it is desired to carry out a hydrogenation, the hydrogenation iscarried out preferably on mixtures of products containing compoundshaving unsaturation prepared by the above named Diels-alder reactions.Thus, when carrying out the hydrogenation on a mixture of productscontaining compounds resulting from the catalytic process and having thestructures: ##STR84## wherein R₃, R₄ and R₅ are defined as above,compounds having the structures: ##STR85## will be produced.

When carrying out the hydrogenation on a mixture of products containingthe compounds resulting from the noncatalytic, thermal process andhaving the structures: ##STR86## the compounds having the structures:##STR87## will be produced.

In either case, it is preferably to carry out the hydrogenation atpressures of from about 20 psig up to about 2,000 psig with a pressurerange of from about 40 up to about 80 psig being preferred. It is alsopreferable for the reaction to be carried out in the presence of acatalyst such as Raney Nickel, palladium on carbon, palladium on calciumcarbonate, palladium on barium surfate and platinum. When using thepalladium-salt catalyst, it is preferred to use from about 3% up toabout 12% palladium on salt, for example 5% palladium on calciumcarbonate.

Thus, the reaction sequence which is embodied within our invention whenusing the catalytic procedure may be illustrated as follows: ##STR88##wherein one of R₃ and R₄ is hydrogen and the other of R₃ or R₄ ismethyl; wherein R₅ represents C₁ -C₄ lower alkyl; wherein R' representsC₁ -C₃ alkyl; and wherein M+N equals three with M being equal to one ortwo and N being equal to one or two.

Furthermore, the reaction sequence which is embodied within ourinvention when using the high temperature noncatalytic thermalDiels-alder reaction may be illustrated as follows: ##STR89## whereinR₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined above.

The following tables set forth the products covered by our invention andthe alkyl acrylate precursor reactant starting materials to be reactedwith the methylcyclopentadienes to produce said products and in additionsets forth the organoleptic properties of the products of our invention:

                                      TABLE I    __________________________________________________________________________    Alkylacrylate                Reaction Product                             Reaction Product    Reactant    Names        Structures    __________________________________________________________________________    Methylcrotonate (catalytic Diels- alder reaction)                Methyl ester of 1,3- and 3,5-dimethyl norbornene-2- carboxylic                 acid                              ##STR90##                             and                              ##STR91##    Methylcrotonate (catalytic Diels- alder reaction)                Methyl ester of 1,3- and 3,5-dimethyl norbornane-2- carboxylic                 acid                              ##STR92##                             and                              ##STR93##    Ethylcrotonate (catalytic Diels- alder reaction)                Ethyl ester of 1,3- and 3,5-dimethyl norbornene-2- carboxylic                acid                              ##STR94##                             and                              ##STR95##    Ethylacrylate (catalytic Diels- alder reaction)                Ethyl ester of 1- and 5-methyl- 5-norbornene-2- carboxylic                acid                              ##STR96##                             and                              ##STR97##    Ethylacrylate (catalytic Diels- alder reaction)                Ethyl ester of 1- and 5-methyl- norbornane-2- carboxylic                              ##STR98##                             and                              ##STR99##    n-Butylacrylate (catalytic Diels- alder reaction)                n-Butyl ester of 1- and 5-methyl- 5-norbornene-2- carboxylic                acid                              ##STR100##                             and                              ##STR101##    Ethylmethacrylate (catalytic Diels- alder reaction)                Ethyl esters of 1,2- and 2,5- dimethyl-5-nor- bornene-2-carbox                y- lic acid                              ##STR102##                             and                              ##STR103##    Ethylcrotonate (catalytic Diels- alder reaction)                Ethyl ester of 1,3-and 3,5-dimethyl norbornane-2-carboxylic                acid                              ##STR104##                             and                              ##STR105##    Isopropylacrylate (thermal non-catalytic Diels-alder reaction)                Isopropyl ester of 5- and 6-methyl-5- norbornane-2-carboxy-                lic acid                              ##STR106##                             and                              ##STR107##    Ethylacrylate                Ethyl esters of 1-; 4-; 5-; and 6-methyl- 5-norbornane-2-                carboxylic acid                              ##STR108##                              ##STR109##                              ##STR110##                             and                              ##STR111##    Ethylacrylate (thermal Diels- alder non-catalytic reaction)                Ethyl ester of 1-; 4-; 5-; and 6-methyl- norbornane-2-                carboxylic acid                              ##STR112##                              ##STR113##                              ##STR114##                             and                              ##STR115##    Ethylcrotonate (non-catalytic thermal Diels- alder reaction)                Ethyl esters of 3,5- and 3,6-di- methyl-5-norbornane-                2-carboxylic acid                              ##STR116##                             and                              ##STR117##    __________________________________________________________________________

                                      TABLE II    __________________________________________________________________________                                     Smoking    Reaction Product               Fragrance  Flavor     Tobacco Flavor    Name       Properties Properties Properties    __________________________________________________________________________    Methyl ester of               A fruity, ba-                          A burnt fruit                                     Sweet, fruity,    1,3- and 3,5-               nana, creamy                          aroma and  berry-like, woody    dimethyl norbor-               aroma with taste at 0.1                                     aroma prior to    nene-2-carboxylic               camphoraceous                          ppm        smoking and a    acid       and minty             sweet, fruity    (catalytic Diels-               undertones            aroma on smoking    alder reaction)                  both in the main-                                     and sidestreams    Methyl ester of               A fruity, cam-                          A fruity and                                     Prior to smoking    1,3- and 3,5-               phoraceous and                          blackberry-                                     a sweet, woody,    dimethyl norbor-               herbaceous like aroma and                                     spicy, cooling    nane-2-carboxylic               aroma      taste at 0.1                                     and clove-like    acid                  ppm        aroma profile;    (catalytic Diels-                and on smoking    alder reaction)                  a sweet, spicy,                                     cooling and                                     woody aroma and                                     taste in both                                     the main stream                                     and the side                                     stream    Ethyl ester of               A sweet, spicy                          A sweet, fruit,                                     A sweet, fruity,    1,3- and 3,5-               herbal, woody,                          berry-like,                                     berry, spicy,    dimethyl norbor-               eucalyptol-like                          spicy, black                                     cinnamon bark-    nene-2-carboxylic               aroma profile                          pepper-like,                                     like and clove-    acid       with a dis-                          herbaceous,                                     like aroma and    (catalytic Diels-               tinct calamnus                          clove-like taste profile    alder reaction)               undertone with                          aroma and  prior to and on               tagett-like                          taste profile                                     smoking in the               nuances on at 10 ppm  main stream and               dryout     causing it to                                     the side stream                          be useful in                          blueberry,                          tobacco, clove                          and raspberry                          flavor food-                          stuffs    Ethyl ester of               A sweet, fruity                          A sweet, fruity                                     A fruity, banana-    1- and 5-methyl-               (banana-like)                          red berry-like,                                     like, green and    5-norbornene-2-               creamy and raspberry and                                     strawberry-like    carboxylic acid               minty aroma                          seedy aroma and                                     aroma and taste    (catalytic Diels-               profile with                          taste profile                                     both prior to    alder reaction)               the minty  with an addi-                                     and on smoking               notes outstand-                          tional strawberry                                     in the main               ing on dryout                          taste nuance at                                     stream and in                          0.02 ppm causing                                     the side stream                          it to be useful                          in red berry,                          cherry, rasp-                          berry and straw-                          berry flavors    Ethyl ester of               A fruity, bana-                          A sweet, fruity,                                     A sweet, fruity,    1- and 5-methyl-               an like, and                          raspberry, ver-                                     "juicyfruit",    5-norbornane-2-               creamy aroma                          mouth-like and                                     woody, piney,    carboxylic acid               profile    blueberry aroma                                     and blueberry    (catalytic Diels-     with fruit,                                     aroma and    alder reaction)       raspberry and                                     taste profile                          blueberry taste                                     prior to and                          characteristics                                     on smoking in                          at 0.01 ppm and                                     the mainstream,                          at 1 ppm causing                                     and in the side                          it to be useful                                     stream                          for vermouth,                          blueberry and                          raspberry flavors                          and mouthwash and                          toothpaste                          flavors    n-Butyl ester of               A balsamic and                          A fruity, straw-                                     An earthy,    1- and 5-methyl-               rum/butterscotch                          berry, blueberry                                     mushroom aroma    5-norbornene-2-               aroma profile                          and balsamic                                     prior to and    carboxylic acid       aroma profile                                     on smoking    (catalytic Diels-     with blueberry,    alder reaction)       balsamic and                          bitter taste                          characteristics                          at 2 ppm    Ethyl esters of               A green, minty,                          A fruit, rasp-                                     A sweet, green,    1,2- and 2,5-               borneol-like,                          berry and seedy                                     herbaceous,    dimethyl-5-nor-               spicy, somewhat                          aroma and taste                                     dill and fruity    bornene-2-carboxy-               medicinal aroma                          profile with                                     aroma and taste    lic acid   profile remin-                          additional profile both    (catalytic Diels-               iscent of  bitter taste                                     prior to and    alder reaction)               pepacuana boric                          nuances at 0.2                                     on smoking in               extract    ppm        mainstream and                                     in the side                                     stream    Ethyl esters of               A fruity,  A fruity, blue-    1,3- and 3,5-               piney, herb-                          berry and    dimethyl-5-nor-               aceous and herbaceous aroma    bornane-2-carboxy-               cassis aroma                          character with a    lic acid   profile with                          sweet, fruity    (catalytic Diels-               calamnus under-                          and blueberry    alder reaction)               tones      flavor charac-                          teristic at                          0.02 parts per                          million    Isopropyl  A green, fruity                          A camphoraceous    ester of 5- and               aroma      blueberry and    6-methyl-5-nor-       wild strawberry    bornane-2-car-        aroma and flavor    boxylic acid          profile at 0.1    (thermal non-         ppm    catalytic    Diels-alder    reaction)    Ethyl esters of               A sweet, fruity,                          Sweet, fruity,                                     A fruity,    1-; 4-; 5-; and 6-               minty aroma                          raspberry  natural    methyl-5-nor-         aroma with tobacco    bornane-2-car-        strawberry aroma and    boxylic acid          nuances    taste both    (thermal non-                    prior to and    catalytic                        on smoking    Diels-alder                      in the main    reaction)                        stream and                                     the side                                     stream    Ethyl ester of               A fruity, banana                          A raspberry                                     A sweet,    1-; 4-; 5-; and 6-               and creamy aroma                          aroma and  fruity "juicy-    methyl-nor-               profile    taste with fruit" aroma    bornane-2-car-        blueberry  and taste    boxylic acid          nuances at profile both    (thermal non-         0.05 ppm   prior to and    catalytic                        on smoking    Diels-alder                      in the main    reaction)                        stream and in                                     the side                                     stream    Ethyl esters of               An intense,                          A sweet, fruity,                                     A sweet,    3,5- and 3,6-               fruity, straw-                          clove-like aroma                                     fruity, spicy    dimethyl-  berry-like,                          and taste pro-                                     clove-like    5-norbornane-2-               raspberry-like,                          file at 4 ppm                                     aroma and    carboxylic acid               reseda body-          taste both    (thermal non-               like aroma but        prior to and    catalytic  does not have         on smoking    Diels-alder               cagett nuances        in the main    reaction)                        stream and                                     the side                                     stream    __________________________________________________________________________

When the norbornane derivatives of our invention are used as food flavoradjuvants, the nature of the co-ingredients included with each of thesaid norbornane derivatives in formulating the product composition willalso serve to alter, modify, augment or enhance the organolepticcharacteristics of the ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually to, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers ofsoftening agents, e.g., glycerine; and a flavor composition whichincorporates one or more of the norbornane derivatives of our invention,and in addition, sweetening agents which may be sugars, includingsucrose or dextrose and/or artificial sweeteners such as cyclamates orsaccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene(2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents includes emulsifying agents, e.g., fatty acidssuch as capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tri-basic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include aldehydes, esters,natural oils, alcohols, sulfides, ketones, lactones, carboxylic acidsand hydrocarbons such as heliotropin, terpinenol-4, benzaldehyde,anisaldehyde, phenyl acetaldehyde, benzyl formate, benzyl acetate,cis-3-hexenyl benzoate, methyl hexanoate, hexanal, eucalyptol, eugenol,acetaldehyde, ethyl acetate, ethyl butyrate, turpentine gum oil,limonene, gum camphor, isobornyl acetate, borneol, cinnamic aldehyde,cuminic aldehyde, furfural, methyl cinnamate, cassia oil, vanillin,maltol, parahydroxybenzyl acetate, dimethyl sulfide, alphaionone, aceticacid, isobutyl acetate, acetone, butyric acid, formic acid, valericacid, amyl acetate, amyl butyrate, anethol, benzyl salicylate, diacetyl,dimethyl anthranilate, ethyl methylphenylglycidate, ethyl succinate,ethyl valerate, geraniol, cis-3-hexen-1-ol, 2-hexenyl acetate, 2-hexenylbutyrate, hexyl butyrate, 4-(p-hydroxyphenyl)-2-butanone, betaionone,isobutyl cinnamate, jasmine, lemon essential oil, methyl butyrate,methyl caproate, methyl disulfide, methyl p-naphthyl ketone, orrisbutter, rose absolute, terpenyl acetate, gamma-undecalactone, vanillaand alcohol.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the norbornane derivatives ofour invention by not covering or spoiling the organoleptic properties(aroma and/or taste) thereof; (ii) be non-reactive with the norbornanederivatives of our invention and (iii) be capable of providing anenvironment in which the norbornane derivatives can be dispersed oradmixed to provide a homogeneous medium. In addition, selection of oneor more flavoring adjuvants, as well as the quantities thereof willdepend upon the precise organoleptic character desired in the finishedproduct. Thus, in the case of flavoring compositions, ingredientselection will vary in accordance with the foodstuff, chewing gum,medicinal product or toothpaste to which the flavor and/or aroma are tobe imparted, modified, altered or enhanced. In contradistinction, in thepreparation of solid products, e.g. simulated foodstuffs, ingredientscapable of providing normally solid compositions should be selected suchas various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount ofnorbornane derivatives employed in a particular instance can vary over arelatively wide range, depending upon the desired organoleptic effectsto be achieved. Thus, correspondingly, greater amounts would benecessary in those instances wherein the ultimate food composition to beflavored is relatively bland to the taste, whereas relatively minorquantities may suffice for purposes of enhancing the composition merelydeficient in natural flavor or aroma. The primary requirement is thatthe amount selected to be effective, i.e., sufficient to alter, modify,or enhance the organoleptic characteristics of the parent composition,whether foodstuff per se, chewing gum, per se, medicinal product per se,toothpaste per se, or flavoring composition.

The use of insufficient quantities of norbornane derivatives will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities prove needlessly costly and, in extremecases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of norbornane derivativesranging from a small but effective amount, e.g., 0.01 parts per millionup to about 100 parts per million based on total composition aresuitable. Concentrations in excess of the maximum quantity stated arenot normally recommended, since they fail to prove commensurateenhancement of organoleptic properties. In those instances, wherein thenorbornane derivatives are added to the foodstuff as an integralcomponent of a flavoring composition, it is, of course, essential thatthe total quantity of flavoring composition employed be sufficient toyield an effective norbornane derivative concentration in the foodstuffproduct.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the norbornane derivatives inconcentrations ranging from about 0.01% up to about 15% by weight basedon the total weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the norbornane derivatives with, forexample, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spray-drying the resultant mixture whereby to obtain theparticular solid product. Pre-prepared flavor mixes in powder form e.g.,a fruit-flavored powder mix are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like and norbornane derivativesin a dry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the norbornane derivatives ofour invention, the following adjuvants:

Heliotropin;

Terpinenol-4;

Benzaldehyde;

Anisaldehyde;

Phenylacetaldehyde;

Benzyl formate;

Benzyl acetate;

Cis-3-hexenyl benzoate;

Methyl hexanoate;

Hexanal;

Eucalyptol;

Eugenol;

Acetaldehyde;

Ethyl acetate;

Ethyl butyrate;

Turpentine gum oil;

Limonene;

Gum camphor;

Isobornyl acetate;

Borneol;

Cinnamic aldehyde;

Cuminic aldehyde;

Furfural;

Methyl cinnamate;

Cassia oil;

Vanillin;

Malto;

Paranydroxybenzylacetone;

Dimethyl sulfide;

Alpha-ionone;

Acetic acid;

Isobutyl acetate;

Acetone;

Butyric acid;

Formic acid;

Valeric acid;

Amyl acetate;

Amyl butyrate;

Anethol;

Benzyl salicylate;

Diacetyl;

Dimethyl anthranilate;

Ethyl methylphenylglycidate;

Ethyl succinate;

Ethyl valerate;

Geraniol;

Cis-3-hexen-1-ol;

2-Hexenyl acetate;

2-Hexenyl butyrate;

Hexyl butyrate;

4-(p-Hydroxyphenyl)-2-butanone;

Beta-ionone;

Isobutyl cinnamate;

Jasmine;

Lemon essential oil;

Methyl butyrate;

Methyl capronate;

Methyl disulfide;

Methyl p-naphthyl ketone;

Orris butter;

Rose absolute;

Terpenyl acetate;

Gamma-undecalactone;

Vanilla; and

Alcohol.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor, as well asmethods of making the same which overcome problems heretoforeencountered in which desired spicy, cooling, clove-like, cinnamonbark-like, sweet, fruity, berry-like, juicyfruit, woody, piney,blueberry, banana, green, herbaceous, strawberry-like, and dill flavorcharacteristics of natural tobacco (prior to smoking and, on smoking, inthe mainstream and in the sidestream) as well as cooling effects, arecreated or enhanced or modified or augmented and may be readilycontrolled and maintained at the desired uniform level regardless ofvariations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various desirable natural aromatic tobacco flavoringcharacteristics with spicy, cooling, clove-like, cinnamon bark-like,sweet, fruity, berry-like, juicyfruit, woody, piney, blueberry, banana,green, herbaceous, strawberry-like and dill notes may be imparted tosmoking tobacco products and may be readily varied and controlled toproduce the desired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient one ormore norbornane derivatives of our invention.

In addition to the norbornane derivatives of our invention otherflavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in mixture with thenorbornane derivatives as follows:

I. Synthetic Materials

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho-(2,1-b-)-furan

4-Hydroxyhexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372, issued on 6-29-71.

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil.

An aroma and flavoring concentrate containing one or more norbornanederivatives of our invention and, if desired, one or more of the aboveindicated additional flavoring additives may be added to the smokingtobacco material, to the filter or to the leaf or paper wrapper. Thesmoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accodance with taste but insofaras enhancement or the imparting of spicy and/or cooling and/orclove-like and/or cinnamon bark-like and/or sweet and/or fruity and/orberry-like and/or juicyfruit and/or woody and/or piney and/or blueberryand/or banana and/or green and/or herbaceous and/or strawberry-likeand/or dill notes, we have found that satisfactory results are obtainedif the proportion by weight of the sum total of norbornane derivative(s)to smoking tobacco material is between 50 ppm and 1,500 ppm(0.015%-0.15%). We have further found that satisfactory results areobtained if the proportions by weight of the sum total of norbornanederivative used to flavoring material is between 1,500 and 15,000 ppm(0.15%-1.5%).

Any convenient method for incorporating the norbornane derivative(s)into the tobacco product may be employed. Thus, the nobornanederivative(s) taken alone or along with other flavoring additives may bedissolved in a suitable solvent such as ethanol, diethyl ether and/orvolative organic solvents and the resulting solution may either bespread on the cured, cased and blended tobacco material or the tobaccomaterial may be dipped into such solution. Under certain circumstances,a solution of the norbornane derivative(s) taken alone or taken furthertogether with other flavoring additives as set forth above, may beapplied by means of a suitable applicator such as a brush or roller onthe paper or leaf wrapper for the smoking product, or it may be appliedto the filter by either spraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated by have the norbornanederivative(s) in excess of the amounts or concentrations above indicatedso that when blended with other tobaccos, the final product will havethe percentage within the indicated range.

In accordance with one specific example of our invention an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethanolsolution of the mixture of 1,3-and 3,5-dimethyl-2-norbornane carboxylicacid methyl esters having the structures: ##STR118## in an amount ofmixture to provide tobacco composition containing 800 ppm by weight ofthe mixture of the two esters on a dry basis. Thereafter the alcohol isremoved by evaporation and the tobacco is manufactured into cigarettesby the usual techniques. The cigarette when treated as indicated has adesired and pleasing aroma which is detectable in the mainstream and thesidestream when the cigarette is smoked. This aroma is described asbeing sweeter, more aromatic, more tobacco-like having sweet, spicy,cooling, woody and clove-like notes.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products, formed from sheeted tobacco dust or fines mayalso be used. Likewise, the norbornane derivative(s) of our inventioncan be incorporated with materials such as filter tip materials (e.g.cellulose acetate filters wherein spicy, cooling, clove-like, cinnamonbark-like, sweet, fruity, berry-like, juicyfruit, woody, piney,blueberry, banana, green, herbaceous, strawberry-like and/or dilleffects are desired), seam paste, packaging materials and the like whichare used along with tobacco to form a product adapted for smoking.Furthermore, the norbornane derivative(s) can be added to certaintobacco substitutes of natural or synthetic origin (e.g., dried lettuceleaves) and, accordingly, by the term "tobacco" as used throughout thisspecification is meant any composition intended for human consumption bysmoking or otherwise, whether composed of tobacco plant parts orsubstitute materials or both.

The norbornane derivative(s) and one or more auxiliary perfumeingredients, including, for example, hydrocarbons, alcohols, ketones,aldehydes, nitriles, esters, lactones or cyclic esters, syntheticessential oils and natural essential oils, may be admixed so that thecombined odors of the individual components produce a pleasant anddesired fragrance, particularly and preferably in fruity, banana,creamy, camphoraceous, herbaceous, strawberry-like, raspberry-like,reseda body-like, sweet, spicy, woody, eucalyptol-like, tagett-like,rum/butterscotch, balsamic, green, and/or minty fragrances. Such perfumecompositions usually contain (a) the main note or the "bouquet": orfoundation stone of the composition; (b) modifiers which round off andaccompany the main note; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation and substances which retard evaporation; and (d) topnoteswhich are usually low boiling fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the norbornane derivative(s) of our invention can be used to alter,modify or enhance the aroma characteristics of a perfume composition,for example by utilizing or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of norboranane derivative(s) of our invention which will beeffective in perfume compositions as well as perfumed articles andcolognes depends on many factors, including the other ingredients, theiramounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.01% of norbornanederivative(s) or even less (e.g., 0.005%) can be used to impart afruity, banana, creamy, camphoraceous, strawberry-like, raspberry-like,reseda body-like, herbaceous, sweet, spicy, woody, eucalyptol-like,rum/butterscotch, balsamic, green, minty, borneol-like, tagett-likeand/or medicinal odor with camphor, minty and calamnus-like nuances tosoaps, detergents (including anionic, nonionic, cationic andzwitterionic solid or liquid detergents), cosmetics, fabric softeners,dryer-added fabric softener articles, fabric whiteners and opticalbrighteners or other products. The amount employed can range up to 70%of the fragrance components and will depend on considerations of cost,nature of the end product, the effect desired on the finished productand the particular fragrance sought.

The norbornane derivative(s) of our invention are useful (taken alone ortogether with other ingredients in perfume compositions) in detergentsand soaps, space odorants and deodorants, perfumes, colognes, toiletwater, bath preparations, such as lacquers, brilliantines, pomades andshampoos; cosmetic preparations, such as creams, deodorants, handlotions and sun screens; powders such as talcs, dusting powders, facepowders and the like. As little of 0.005% of the nobornane derivative(s)(in the ultimate perfumed article) will suffice to impart an intense,fruity, banana, creamy, camphoraceous, strawberry-like, raspberry-like,reseda body-like, herbaceous, sweet, spicy, woody, eucalyptol-like,rum/butterscotch, balsamic, green, minty, borneol-like, tagett-likeand/or medicinal note to various types of perfumed articles. Generallyno more than 3% of the norbornane derivative(s) based on the ultimateend product (perfumed article) is required.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the norbornanederivative(s). The vehicle can be a liquid such as a non-toxic alcohol,a non-toxic glycol or the like. The carrier can also be an absorbentsolid, such as a gum (e.g., gum arabic), or components for encapsulatingthe composition (such as gelatin).

It will thus be apparent that the norbornane derivative(s) of ourinvention can be utilized to alter, modify or enhance sensoryproperties, particularly organoleptic properties such as flavor(s)and/or fragrance(s) of a wide variety of consumable materials.

The following examples serve to illustrate processes for specificallyproducing the norbornane derivative(s) useful in our invention.

The following examples also serve to illustrate specific embodiments ofour invention

It will be understood that these examples are illustrative and theinvention is to be considered to be restricted thereto only as indicatedin the appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF 1,3-DIMETHYL-5-NORBORNENE-2-CARBOXYLIC ACIDMETHYL ESTER AND 3,5-DIMETHYL-5-NORBORNENE-2-CARBOXYLIC ACID METHYLESTER (CATALYTIC DIELS-ALDER REACTION)

Reaction: ##STR119##

Into a 3 liter flask equipped with stirrer, thermometer, condenser,addition funnel and cooling bath are charged 1000 ml toluene, 500 gramsmethyl crotonate, 45 grams ethyl aluminum dichloride. The resultingmixture is cooled to 20°-25° C. Over a period of 50 minutes whilemaintaining the reaction mass at 24°-25° C., 320 grams of methylcyclopentadiene (mixture of 1-methyl-1,3-cyclopentadiene and2-methyl-1,3-cyclopentadiene (50% in toluene solution)) is added. Afterthe completion of the addition of the methyl cyclopentadiene mixture,the reaction mass is stirred for a period of 3 hours at 21°-125° C. Atthe end of the three hour period the reaction mass is heated to 40° C.and the temperature is maintained at 40° C. for a period of 2.7 hours.At the end of the 207 hour period the reaction mass is cooled to 20° C.and is poured into one liter of 10% hydrochloric acid solution. Thereaction mass now exists in two phases. The aqueous phase is separatedfrom the organic phase. The aqueous phase is extracted with 500 mltoluene extract and organic phase are combined. The resulting organicphase is then washed as follows:

One 1 liter portion water;

One 1 liter portion saturated sodium carbonate;

One 1 liter portion water.

The toluene is then removed under reduced pressure. The resultingorganic material is then distilled in a 12 inch Goodloe column yieldingthe following fractions:______________________________________ VaporLiquid Weight ofFraction Temp. Temp. mm/Hg. Reflux FractionNo. (°C.)(°C.) Pressure Ratio (g.)______________________________________1 41/4370/71 2.1/2.0 9:1 21.02 48 72 2.0 9:1 22.63 45 73 2.0 9:1 21.84 48 732.0 9:1 22.25 48 72 2.0 9:1 16.76 48 73 2.0 9:1 22.07 49 74 2.0 9:119.98 49 86 2.0 9:1 20.59 50/35 95/205 2.5/1.0 9:112.0______________________________________

Fractions 4-7 are bulked for purposes of flavor evaluation. The bulkedfractions 4-7 as analyzed by NMR, IR and mass spectral analysis containa mixture of compounds having the structures: ##STR120## Fractions 4-7bulked has a burnt fruit aroma and flavor characteristic at 0.1 ppm.

Fractions 4-7 bulked has a fruity, banana, creamy aroma withcamphoraceous, minty undertones.

FIG. 1 represents the GLC profile for the reaction product of Example Icontaining the compounds having the structures: ##STR121##

FIG. 2A represents the NMR spectrum for fraction 8 of the foregoingdistillation containing only the compound having the structure:##STR122##

FIG. 2B represents the NMR spectrum for fraction 2 of the foregoingdistillation containing the compound having the structure: ##STR123##

FIG. 3A represents the infrared spectrum for fraction 8 of the foregoingdistillation containing only the compound having the structure:##STR124##

FIG. 3B represents the infrared spectrum for fraction 2 of the foregoingdistillation containing only the compound having the structure:##STR125##

FIG. 4 represents the mass spectrum for the reaction product of ExampleI containing the compounds having the structures: ##STR126##

EXAMPLE II PREPARATION OF 1,3-DIMETHYL-5-NORBORNANE-2-CARBOXYLIC ACIDMETHYL ESTER AND 3,5-DIMETHYL-5-NORBORNANE2-CARBOXYLIC ACID METHYL ESTER

Reaction: ##STR127##

Into a 500 ml pressure bottle held in a Parr shaker is charged 100 mlisopropyl alcohol and 160 grams (0.89 moles) of the methylcyclopentadiene/methyl crotonate adduct having the structures:##STR128## prepared according to Example I and 4 grams of Raney Nickel.The Parr shaker is purged with hydrogen and charged to 50 psig. Shakingis begun and the Parr shaker is recharged with hydrogen when necessaryin order to maintain the pressure at 50 psig. A total pressure drop of74 pounds of hydrogen is observed. A GLC profile (conditions: Carbowaxcolumn programmed at 80°-220° C. at 8° C. per minute) indicates somechange. NMR analysis indicates that all of the olefin is consumed.

At the end of the reaction the pressure bottle is opened and the RaneyNickel catalyst is filtered and the solvent is stripped off underreduced pressure. The resulting residue is distilled yielding 122 gramsof product. The distillation takes place on a 12"×2' Goodloe columnyielding the following fractions:______________________________________Vapor Liquid Weight ofFraction Temp. Temp. mm/Hg. Reflux FractionNo.(°C.) (°C.) Pressure Ratio (g.)______________________________________137/41 72/75 .65/.8 9:1 212 42 76 .65 9:1 253 43 78 .65 9:1 234 44 80 .89:1 195 45 95 .8 9:1 226 60 215 .8 9:112______________________________________

NMR, mass spectral and IR analysis yields the information that theresulting product is a mixture of the compounds having the structures:##STR129##

FIG. 5 sets forth the GLC profile for the reaction product producedaccording to this example. FIG. 6A sets forth the NMR spectrum for peak1 of the GLC profile which consists essentially of the compound havingthe structure: ##STR130##

FIG. 6B sets forth the NMR spectrum for fraction 6 of the foregoingdistillation which consists essentially of the compound having thestructure: ##STR131##

FIG. 7A sets forth the infrared spectrum for peak 1 of the foregoing GLCprofile which consists essentially of the compound having the structure:##STR132##

FIG. 7B sets forth the infrared spectrum for fraction 6 of the foregoingdistillation which consists essentially of the compound having thestructure: ##STR133##

FIG. 8 sets forth a mass spectrum for the reaction product of thisexample which contains the compounds having the structures: ##STR134##

The resulting mixture, from a food flavor standpoint, has a fruity,blueberry aroma and flavor characteristic at 0.1 ppm. The resultingmixture from a fragrance standpoint, has a fruit, camphoraceous andherbaceous aroma profile.

The mixture of this example also has a sweet, woody, spicy, cooling andclove-like aroma profile prior to smoking and a sweet, spicy, coolingand woody aroma and taste profile on smoking tobacco articles in boththe mainstream and the sidestream.

EXAMPLE III PREPARATION OF THE ETHYL ESTER OF 1,3 and 3,5-DIMETHYL5-NORBORNENE CARBOXYLIC ACID (CATALYTIC DIELS-ALDER REACTION)

Reaction: ##STR135##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,condenser, addition funnel, nitrogen purge and cooling bath are added1000 ml toluene; 600 grams ethyl crotonate; and 50 grams of a 25%solution of ethyl aluminum dichloride in anhydrous toluene. Theresulting mixture is cooled to 20°-25° C. and over a period of 3 hourswhile maintaining the temperature of the reaction at 20°-23° C., 378grams of methyl cyclopentadiene mixture containing compounds having thestructures: ##STR136## are added.

The reaction mass is then poured into one liter of a 10% aqueoushydrochloric acid solution. The reaction mass now exists in two phases;an aqueous phase and an organic phase. The aqueous phase is removed fromthe organic phase and the aqueous phase is extract with one 500 mlvolume of toluene. The toluene and organic phases are combined andwashed as follows:

A. One 1 liter portion of water;

B. One 1 liter portion of saturated sodium bicarbonate solution; and

C. One 1 liter portion of water.

The solvent is stripped off via vacuum. The resulting material is thendistilled using a 12 inch Goodloe column yielding the followingfractions:______________________________________ Vapor Liquid WeightofFraction Temp. Temp. mm/Hg. Reflux FractionNo. (°C.) (°C.) PressureRatio (g.)______________________________________1 32 53 2.0 9:1 43.82 3062 1.0 9:1 43.03 38 73 1.8 9:1 38.34 40 73 .86 9:1 37.55 44 74 .86 9:144.56 44 76 .86 9:1 37.07 44 82 .86 9:1 52.78 44 90 .86 9:1 43.69 44 102.85 9:1 48.710 55 130 .85 9:1 16.211 65 220 2.5 9:148.8______________________________________

NMR, IR and mass spectral analysis yields the information that thereaction product contains compounds having the structures: ##STR137##

FIG. 9 sets forth the GLC profile prior to distillation of the resultingreaction product.

FIG. 10A sets forth the NMR spectrum for fraction 10 of the foregoingdistillation containing only the product having the structure:##STR138##

FIG. 10B is the NMR spectrum for the compound contained in fraction 6 ofthe foregoing distillation, having the structure: ##STR139##

FIG. 11A is the infrared spectrum for the compound of fraction 10 of theforegoing distillation having the structure: ##STR140##

FIG. 11B is the infrared spectrum for the compound contained in fraction6 of the foregoing distillation, having the structure: ##STR141##

FIG. 12 is the mass spectrum for the mixture of compounds produced bythe foregoing reaction having the structures: ##STR142##

Bulked fractions 5-11 containing the compounds having the structures:##STR143## from a fragrance standpoint has a sweet, spicy, herbal,woody, eucalyptol-like aroma with distinct calamnus undertones.

Bulked fractions 5-11 from a food flavor standpoint has a sweet, fruity,berry-like, spicy, black pepper-like, herbaceous and clove-like aromaand taste profile at 10 ppm causing said bulked fractions to be usefulin blueberry flavored tobacco (cloves) flavor and raspberry flavor.

Bulked fractions 5-11 from a tobacco flavor standpoint has a sweet,fruity, berry, spicy, cinnamon bark-like and clove-like aroma and tasteprofile both prior to and on smoking in the mainstream and in thesidestream of smoking tobacco articles such as cigarettes and cigars.

EXAMPLE IV PREPARATION OF ETHYL ESTERS OF 1- and5-METHYL-5-NORBORNENE-2-CARBOXYLIC ACIDS (CATALYTIC DIELS-ALDERREACTION) ##STR144##

Into a three liter flask equipped with thermometer, stirrer, condenser,addition funnel, cooling bath and nitrogen purge are placed one gram ofhydroquinone, 1000 ml toluene and 50 grams of 25% ethyl aluminumdichloride dissolved in anhydrous toluene. The reaction mass is cooledto about 10° C. and, over a period of 30 minutes, 600 grams of ethylacrylate is added to the resulting mixture. During the addition thetemperature of the mixture is maintained at between 10° C. and 14° C.

Over a period of three hours while maintaining the reaction temperatureat 20°-23° C., 389 grams of a mixture of 1-methyl-1,3-cyclopentadieneand 2-methyl-1,3-cyclopentadiene is added to the reaction mixture. Atthe end of the three hour period GLC analysis indicates the reaction tobe complete.

The resulting reaction mass is poured into one liter of 10% aqueoushydrochloric acid. The reaction mass now exists in two phases; anorganic phase and an aqueous phase. The aqueous phase is separated fromthe organic phase and the organic phase is washed as follows:

A. One 1 liter portion of water;

B. One 1 liter portion of saturated sodium bicarbonate solution;

C. One 1 liter portion of water;

D. One 1 liter portion of water.

The pH of the resulting washing is about six.

The resulting organic layers are combined and the toluene is strippedoff under vacuum. Calcium carbonate and primol® is added to the reactionmass and the reaction mass is distilled yielding the following fractionson a 12 inch Goodloe column:______________________________________ VaporLiquid Weight ofFraction Temp. Temp. mm/Hg. Reflux FractionNo. (°C.)(°C.) Pressure Ratio (g.)______________________________________1 48/4863/65 3.0/3.0 9:1 23.82 50 64 3.0 9:1 19.33 50 64 2.8 9:1 20.54 53 642.6 9:1 19.15 54 64 2.6 9:1 20.26 55 65 2.8 9:1 19.97 56 66 2.7 9:125.28 54 66 2.5 9:1 21.79 54 66 2.5 9:1 48.610 54 66 2.5 9:1 55.811 5467 2.5 9:1 48.712 57 77 2.5 9:1 59.713 57 77 2.5 9:1 47.214 57 87 2.59:1 58.015 55/58 87/108 2.5/2.5 4:1 33.016 45 110 3.0 4:16.6______________________________________

Fractions 7-12 are bulked and NMR, IR and mass spectral analysis yieldthe information that these fractions consist essentially of a mixture ofcompounds having the structures: ##STR145##

FIG. 13 is the GLC profile of the crude reaction product washed, butbefore distilling. (Conditions: Carbowax column programmed at 80°-122°C. at 8° C. per minute).

FIG. 14 is the GLC profile of fractions 7-12 from the foregoingdistillation, bulked.

FIG. 15A is the NMR spectrum for the compound having the structure:##STR146##

FIG. 15B is the NMR spectrum for the compound having the structure:##STR147##

FIG. 16A is the infrared spectrum for the compound having the structure:##STR148##

FIG. 16B is the infrared spectrum for the compound having the structure:##STR149##

FIG. 17 is the mass spectrum for the mixture of compounds having thestructures: ##STR150##

The mixture of compounds having the structures: ##STR151## from afragrance standpoint has a sweet, fruity (banana-like) and creamy aromaprofile with minty nuances intense on dryout.

From a food flavor standpoint, the resulting mixture has a sweet,fruity, red berry, raspberry and seedy aroma and taste and in addition astrawberry taste at 0.02 ppm. Thus, this material is useful in redberry, cherry, raspberry and strawberry flavored foodstuffs.

The resulting mixture has a fruity, banana, green and strawberry-likearoma and taste both prior to and on smoking smoking tobacco articles inboth the mainstream and the sidestream.

EXAMPLE V PREPARATION OF THE ETHYL ESTERS OF 1-AND 5-METHYLNORBORNANE-2-CARBOXYLIC ACIDS

Reaction: ##STR152##

Into a 500 ml pressure bottle attached to a Parr shaker is charged 200grams (1.11 moles) of the reaction mixture (bulked fractions 7-12)produced according to Example IV consisting essentially of compoundshaving the structures: ##STR153## 5 grams of Raney Nickel and 125 ml ofisopropyl alcohol. The Parr shaker apparatus is purged six times withhydrogen and the 500 ml pressure bottle with contents is pressurized to50 psig. The bottle is closed and shaking is begun and continued untilthe hydrogen uptake ceases. This period of time takes 4.25 hours. The500 ml pressure bottle is recharged when necessary. At the end of thereaction the 500 ml pressure bottle is opened and the reaction mass isfiltered and the solvent stripped in vacuum. The resulting residue isdistilled on a 1" Goodloe-silver column and yields the followingfractions:______________________________________ Vapor Liquid WeightofFraction Temp. Temp. mm/Hg. Reflux FractionNo. (°C.) (°C.) PressureRatio (g.)______________________________________1 54/42 77/77 2.8/.8 9:118.52 42 77 0.75 9:1 22.23 42 78 0.70 9:1 22.04 46 85 0.70 9:1 23.05 5087 1.4 9:1 18.06 50 90 0.8 9:1 21.07 51 111 0.7 9:1 19.08 45 170 0.759:1 23.09 39 214 0.76 9:1 3.0______________________________________

NMR, IR and mass spectral analysis on fractions 1 and 9 yield theinformation that the resulting mixture contains and consists essentiallyof the compounds having the structures: ##STR154##

FIG. 18 is the GLC profile for the resulting reaction mixture.

FIG. 19A is the NMR spectrum for fraction 9 of the foregoingdistillation containing and consisting of the compound having thestructure: ##STR155##

FIG. 19B is the NMR spectrum for fraction 1 of the foregoingdistillation consisting of the compound having the structure: ##STR156##

FIG. 20A is the infrared spectrum for fraction 9 of the foregoingdistillation consisting of the compound having the structure: ##STR157##

FIG. 20B is the infrared spectrum for fraction 1 of the foregoingdistillation consisting of the compound having the structure: ##STR158##

FIG. 21 is the mass spectrum for the reaction product produced accordingto this example containing the mixture of compounds having thestructures: ##STR159##

From a fragrance standpoint bulked fractions 6-8 have a fruity, banana,and creamy aroma profile.

From a food flavor standpoint, bulked fractions 6-8 have a sweet,fruity, raspberry, vermouth-like and blueberry aroma profile with afruity, raspberry and blueberry taste profile at 0.01 ppm and at 1 ppmcausing this mixture to be useful for vermouth, blueberry, raspberrymouthwash and toothpaste flavors.

From a tobacco flavor standpoint, bulked fractions 6-8 has prior to andon smoking in the mainstream and in the sidestream a sweet, fruity,"juicyfruit", woody, piney and blueberry aroma and taste profile.

EXAMPLE VI PREPARATION OF 1- AND 5-METHYL-5-NORBORNENE-2-CARBOXYLIC ACIDn-BUTYL ESTERS (CATALYTIC DIELS-ALDER REACTION) ##STR160##

Into a 3 liter reaction flask equipped with stirrer, thermometer, refluxcondenser, dropping funnel and cooling bath is placed 700 ml toluene and60 grams of ethyl aluminum dichloride. While maintaining the temperatureof the mixture at 20°-25° C., via the dropping funnel is added 300 gramsof n-butyl acrylate over a period of 20 minutes.

While keeping temperature at 20°-25° C. over a 40 minute period, 380grams of a 50% solution of 1-methyl-1,3-cyclopentadiene and2-methyl-1,3-cyclopentadiene is added to the reaction mass.

After about 2 hours an additional 30 grams of ethyl aluminum dichlorideis added and the reaction mass is stirred for another 1.5 hours whilemaintaining the temperature thereof at 20°-25° C.

Reaction mass is then added to 1 liter of 10% hydrochloric acid. Thereaction mass now exists in two phases; an organic phase and an aqueousphase. The organic phase is removed and washed as follows:

A. One 1 liter portion of water;

B. One 1 liter portion of saturated sodium carbonate;

C. One 1 liter portion of water.

The solvent is then removed by vacuum distillation and the resultingproduct is distilled on a 12" Goodloe column yielding the followingfractions:______________________________________ Vapor Liquid WeightofFraction Temp. Temp. mm/Hg. Reflux FractionNo. (°C.) (°C.) PressureRatio (g.)______________________________________1 70/70 107/113 1.0/1.09:1/4:1 16.02 70 113 1.0 4:1 18.03 69 112 1.0 4:1 14.24 69 113 1.0 9:122.65 71 116 1.0 9:1 23.46 71 116 1.0 9:1 21.47 74 116 1.0 9:1 8.78 72121 1.2 9:1 17.49 73 122 1.5 9:1 18.510 74 123 1.2 9:1 18.611 74 123 1.29:1 22.612 82 130 1.3 9:1 18.113 82 133 1.3 9:1 21.214 82 138 1.3 9:122.515 82 140 1.4 9:1 20.316 82 148 1.4 9:1 25.617 82 182 1.2 9:1 23.71884 190 1.2 9:1 6.0______________________________________

NMR, IR and mass spectral analysis yielding the information that theresulting product is a mixture of compounds having the structures:##STR161##

FIG. 22 sets forth the GLC profile for the reaction product.

FIG. 23A sets forth the NMR spectrum for fraction 14 for the foregoingfractional distillation and this fraction consists of compound havingthe structure: ##STR162##

FIG. 23B sets forth the NMR spectrum for fraction 4 of the foregoingdistillation consisting of the compound having the structure; ##STR163##

FIG. 24A sets forth the infrared spectrum for fraction 14 of theforegoing distillation consisting of the compound having the structure:##STR164##

FIG. 24B sets forth the infrared spectrum for fraction 4 of theforegoing distillation consisting of the compound having the structure:##STR165##

FIG. 25 sets forth the mass spectrum for the reaction product containingthe compounds having the structures: ##STR166##

From a fragrance standpoint bulked fractions 2-18 have a balsamic andrum/butterscotch aroma profile.

From a food flavor standpoint, bulked fractions 5-14 have a fruity,strawberry, blueberry, balsamic aroma profile with a blueberry, balsamicand bitter flavor profile at 2 ppm.

From a tobacco flavor standpoint, bulked fractions 5-14 have an earthyand mushroom aroma and taste both prior to and on smoking in themainstream and in the sidestream.

EXAMPLE VII PREPARATION OF ETHYL ESTERS OF 1,2- AND2,5-DIMETHYL-5-NORBORNENE-2-CARBOXYLIC ACIDS (CATALYTIC DIELS-ALDERREACTION) ##STR167##

Into a 5 liter flask equipped with condenser, thermometer, additionfunnel, nitrogen purge and cooling bath are placed 1000 ml toluene, 50grams of ethyl aluminum dichloride and 680 grams of ethyl methacrylate.The resulting mixture is cooled to 20°-25° C. and over a period of 3hours while maintaining the temperature at 23°-24° C. 400 grams of amixture of 1-methyl-1,3-cyclopentadiene and 2-methyl-1,3-cyclopentadieneis added to the reaction mass.

The reaction mass is then poured into 1 liter of 10% aqueoushydrochloric acid. The reaction mass now exists in two phases; anaqueous phase and an organic phase. The aqueous phase is extracted withone 500 ml portion of toluene and the toluene extract is combined withthe organic layer. The resulting organic phase is washed as follows:

A. One 1 liter portion of water;

B. One 1 liter portion of saturated sodium bicarbonate;

C. One 1 liter portion of water.

The resulting product is then stripped of solvent under vacuum. Primol®and Ionox® are then added to the reaction mass. The reaction mass isthen distilled on an 18" Goodloe column yielding the followingfractions:______________________________________ Vapor Liquid WeightofFraction Temp. Temp. mm/Hg. Reflux FractionNo. (°C.) (°C.) PressureRatio (g.)______________________________________1 55/56 84/85 5.5/5.59:1 8.32 60 83 4.0 9:1 41.93 66 84 4.0 9:1 40.04 67 85 4.0 9:1 44.45 6788 4.0 9:1 40.86 67 93 4.0 9:1 40.77 68 101 4.0 9:1 39.18 69 110 4.0 9:151.39 70 125 4.0 9:1 39.410 70 157 4.0 9:1 16.011 72/75 170/220 4.0/4.09:1 10.0______________________________________

NMR, IR and mass spectral analysis yield the information that theresulting product contains two compounds having the structures:##STR168##

These materials are not separable via ordinary commercial physicalseparation procedures or commercial unit operations.

FIG. 26 sets forth the GLC profile for the resulting mixture containingthe compounds having the structures: ##STR169##

FIG. 27 sets forth the NMR spectrum for the mixture of compounds havingthe structures: ##STR170##

FIG. 28 sets forth the infrared spectrum for the compounds having thestructures: ##STR171## in admixture.

FIG. 29 sets forth the mass spectrum for the reaction product asproduced above containing and consisting of the structures: ##STR172##

Bulked fractions 4-10 from a fragrance standpoint has a green, minty,spicy aroma with medicinal nuances and a pepacuana bark extract typeundertone.

From a food flavor standpoint the resulting mixture containing thecompounds having the structures: ##STR173## has a fruity, raspberry andseedy aroma and flavor characteristic with additional bitter flavornuance at 0.2 ppm.

From a tobacco flavor standpoint, the resulting mixture has a sweet,green, herbaceous, dill and fruity aroma and taste both prior to and onsmoking in smoking tobacco in the main stream and in the side stream.

EXAMPLE VII-A PREPARATION OF 1,3- AND 3,5-DIMETHYL NORBORNANE CARBOXYLICACID ESTERS ##STR174##

Into a 500 ml pressure bottle equipped with Parr shaker is placed 200grams of the reaction product of Example III containing the compoundhaving the structures: ##STR175## 100 ml isopropyl alcohol and 5 gramsof Raney nickel. The 500 ml pressure bottle is then closed and placedunder hydrogen pressure. The Parr shaker is shaken under whilemaintaining the hydrogen pressure at 50 psig for a period of 5.5 hoursat a temperature of 20°-30° C. The Parr shaker and pressure bottleapparatus is then opened and the reaction mass is filtered and thesolvent is removed from the reaaction mass. The resulting reactionproduct is then distilled yielding the followingfractions:______________________________________ Vapor Liquid WeightofFraction Temp. Temp. mm. Hg. Reflux FractionNo. (°C.) (°C.) PressureRatio (g.)______________________________________1 53/55 70/73 1.2/1.29:1/9:1 5.72 55 73 1.2 3:1 18.53 54 73 1.2 3:1 15.94 57 74 1.2 3:1 13.0558 74 1.2 3:1 17.36 62 75 1.2 3:1 14.67 64 75 1.5 3:1 25.38 60 80 1.43:1 17.69 58 78 1.2 3:1 24.910 59 80 1.2 3:1 18.511 59 82 1.23:1______________________________________

Fractions 3-8 are bulked and NMR, IR and mass spectral analyses yieldthe information that bulked fractions 3-8 consist of the compoundshaving the structures: ##STR176##

Fraction 1 of the foregoing distillation contains the pure compoundhaving the structure: ##STR177##

Peak 2 of the foregoing GLC analysis consists of the compound having thestructure: ##STR178##

FIG. 31-A is the NMR spectrum for the compound having the structure:##STR179## of fraction 1 of the foregoing distillation.

FIG. 31-B is the NMR spectrum for the compound having the structure:##STR180## of peak 2 of the foregoing GLC profile.

FIG. 32-A is the infrared spectrum for fraction 1 of the foregoingdistillation consisting of the compound having the structure: ##STR181##

FIG. 32-B is the infrared spectrum for peak 2 of the foregoing GLCprofile consisting of the compound having the structure: ##STR182##

FIG. 33-A is the mass spectrum for fraction 1 of the foregoingdistillation consisting of the compound having the structure: ##STR183##

FIG. 33-B is the mass spectrum for peak 2 of the foregoing GLC profileconsisting of the compound having the structure: ##STR184##

EXAMPLE VIII

The following spicy, floral and herbal type formulae areprepared:______________________________________ Parts byWeightIngredient VIII (A) VIII(B)______________________________________Geranium Bourbon 20.020.0Rosemary Oil Spanish 10.0 10.0Lavender Oil Barreme 10.0 10.0ThymeOil White 10.0 10.0Amyl Cinnamic Aldehyde 10.0 10.0Sauge Sclaree French5.0 5.0Sandalwood Oil 5.0 5.0Galbanum Oil 5.0 5.0Patchouli Oil Light 5.05.0Cedarwood Oil Light 15.0 15.0Product produced according 5.0 --toExample III, bulkedfractions 5-11 containingand consisting ofthecompounds having thestructures: ##STR185##and ##STR186##Productproduced according -- 5.0to Example V containingbulked fractions 1-9andconsisting of thecompounds having thestructures: ##STR187##and##STR188##______________________________________

When the compositions of matter prepared according to Example III orExample V are incorporated into the formulae at 5.0% both compositionsof matter add a pleasant fruity, tagette character to these spicy,herbal, floral type perfume formulations.

EXAMPLE IX

A jasmine formulae is produced containing the following ingredients:

    ______________________________________     Ingredients      Parts by Weight    ______________________________________    Isoeugenol        2.0    Benzyl Propionate 10.0    Benzyl Acetate    13.0    Benzyl Alcohol    14.0    Benzyl Benzoate   9.0    Linalool          8.0    Phytol            30.0    Methyl Oleate     4.0    Methyl Palmitate  4.0    Indole - 10% in Diethyl                      1.0    Phthalate    Composition produced                      5.0    according to Example IV    containing bulked    fractions 7-12 and    containing the compounds    having the structures:     ##STR189##    and     ##STR190##

The material produced according to Example IV incorporated into theformula above at 5.0% gives rise to the pleasant fruityness aromaundertone of this jasmine formulation.

EXAMPLE X

The following sweet, floral formula is produced:

    ______________________________________    Ingredients        Parts by Weight    ______________________________________    Hexyl Cinnamic Aldehyde                       12.0    Benzyl Propionate  8.0    Isoeugenol         2.0    Indole - 10% in Diethyl                       1.0    Phthalate    Linalool           8.0    Benzyl Acetate     8.0    Vetivert Oil - Bourbon                       2.0    Gamma Methyl Ionone                       1.0    Phenyl Ethyl Alcohol                       6.0    Patchouli Oil Light                       1.0    Lavandin Abrialis  4.0    Hydroxy Citronellal                       4.0    Bergamot Oil M.P.F.                       6.0    Benzyl Salicylate  13.0    Musk Ambrette      8.0    Coumarin           6.0    Composition of matter pro-                       10.0    duced according to Ex. II    consisting of bulked    fractions 4-6 and consist-    ing the compounds having    the structures:     ##STR191##    and     ##STR192##    ______________________________________

At the 10% level in the foregoing sweet, floral formulation thecompounds having the structures: ##STR193## produced according toExample II contribute an intense and pleasant fruity, floralcy to thissweet, floral fragrance.

EXAMPLE XI

A stable lotion is prepared with the following formulations:

    ______________________________________    Ingredients          Parts by Weight    ______________________________________    poly(N,N-dimethyl-3,5-dimethyl-                         1.0    ene piperidinium chloride)    (Merquat 100, Merck & Co., U.S.A.,    average molecular weight 50,000-    100,000,viscosity in 40% aqueous    solution, 10,000 cps.    cocoamidopropyl dimethyl glycine                         5.7    (betaine)    myristyl dimethylamine oxide                         12.0    stearic monoethanolamide opacifier                         2.0    perfume as indicated in Table III                         0.5    (below) giving rise to the    aroma profiles as indicated in    Table III (below)    water, colour, salts, U.V.                         q.s. to 100    absorber    ______________________________________

Two or three bottle capfuls of the above lotion held under the tapreleasing the water into the bathtub yields a copiously foamed bubblebath with no visible precipitation flocculation, or "bathtub ring" evenusing hard water. Bathing in this bath is found to have a cleansing andpleasing emollient effect on the skin as described above.

When, after immersion in this bath, the body is soaped, rinsed anddried, an even better, more long-lasting emollient, moisturizing effecton the skin is observed. The foam or bubbles are substantiallyunaffected by the soaping step, and no precipitate, flocculate or"bathtub ring", or any bothersome film or coating on the bathtub surfaceis found.

The aroma produced is as is set forth in Table III below:

                  TABLE III    ______________________________________     Product           Aroma Profile    ______________________________________    Product produced according to                       A fruity, banana and    Example I, bulked fractions                       creamy aroma with    4-7 consisting of compounds                       camphoraceous and    having the structures:                       minty undertones.     ##STR194##    and     ##STR195##    Product produced according to                       A fruity, camphoraceous    Example II, bulked fractions                       and herbaceous aroma.    4-6 consisting of the compounds    having the structures:     ##STR196##    and     ##STR197##    Product produced according to                       A sweet, spicy, herbal    Example III, bulked fractions                       woody and eucalyptol-    7 and 8 consisting of the                       like aroma with a dis-    compounds having the structures:                       tinct calamnus undertone     ##STR198##    and     ##STR199##    Product produced according to                       A sweet, fruity (banana)    Example IV, bulked fractions                       creamy and minty aroma    7-12 consisting of compounds                       with the minty nuances    having the structures:                       increasing in intensity                       on dryout.     ##STR200##    and     ##STR201##    Product produced according to                       A fruity, banana and    Example V, bulked fractions                       creamy aroma profile.    6-8 consisting of the compounds    having the structures:     ##STR202##    and     ##STR203##    Product produced according to                       A rum/butterscoth    Example VI, bulked fractions                       and balsamic aroma.    5-14 containing and consisting    of the compounds having the    structures:     ##STR204##    and     ##STR205##    Product produced according to                       A green, minty, borneol-    Example VII, bulked fractions                       like, spicy, somewhat    6-9 consisting of the compounds                       medicinal aroma reminis-    having the structures:                       cent of pepacuana bark                       extract with strong                       pepacuana bark-like under-                       tones.     ##STR206##    and     ##STR207##    Fragrance formulation of                       A spicy, floral, herbal    Example VIII(A)    aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A spicy, floral, herbal    Example VIII(B)    aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A jasmine aroma with a    Example IX         pleasant fruityness.    Fragrance formulation of                       A sweet, floral aroma    Example X          with excellent fruity                       floralcy undertones.    ______________________________________

EXAMPLE XII

The following formulation is prepared with results in properties and usesimilar to those described in Example XI.

    ______________________________________    Ingredients          Parts by Weight    ______________________________________    "Merquat 100"        1.0    cocoamidopropyl dimethyl glycine                         8.0    myristyl dimethyl amine                         16.0    oxide    Perfume ingredient as set forth                         0.8    in Table IV (below) giving    rise to the aroma profiles as    set forth in Table IV (below)    Water                q.s. to 100    ______________________________________

The composition is a clear liquid. Its viscosity may be increased byaddition of a lauric or myristic diethanolamide or a solublepolyethylene glycol ester such as polyethylene glycol 6000. In addition,this composition may be rendered opaque by addition of stearicmonoethanolamide stearate, polyethylene glycol 600 monostearate or aglycol amido stearate such as "Cerasynt 1P".

                  TABLE IV    ______________________________________    Product             Aroma Profile    ______________________________________    Product produced according to                        A fruity, banana and    Example I, bulked fractions                        creamy aroma with    4-7 consisting of compounds                        camphoraceous and    having the structures:                        minty undertones.     ##STR208##    Product produced according to                        A fruity, camphoraceous    Example II, bulked fractions                        and herbaceous aroma.    4-6 consisting of the compounds    having the structures:     ##STR209##    Product produced according to                        A sweet, spicy, herbal    Example III, bulked fractions                        woody and eucalyptol-    7 and 8 consisting of the                        like aroma with a dis-    compounds having the structures:                        tinct calamnus undertone.     ##STR210##    Product produced according to                        A sweet, fruity (banana)    Example IV, bulked fractions                        creamy and minty aroma    7-12 consisting of compounds                        with the minty nuances    having the structures:                        increasing in intensity                        on dryout.     ##STR211##    Product produced according to                        A fruity, banana and    Example V, bulked fractions                        creamy aroma profile.-6-8 consisting of the                        compounds    having the structures:     ##STR212##    Product produced according to                        A rum/butterscotch    Example VI, bulked fractions                        and balsamic aroma.    5-14 containing and consisting    of the compounds having the    structures:     ##STR213##    Product produced according to                        A green, minty, borneol-    Example VII, bulked fractions                        like, spicy, somewhat    6-9 consisting of the compounds                        medicinal aroama reminis-    having the structures:                        cent of pepacuana bark                        extract with strong                        pepacuana bark-like                        undertones.     ##STR214##    Fragrance formulation of                        A spicy, floral, herbal    Example VIII(A)     aroma with pleasant                        fruity tagette character-                        istics.    Fragrance formulation of                        A spicy, floral, herbal    Example VIII(B)     aroma with pleasant                        fruity tagette character-                        istics.    Fragrance formulation of                        A jasmine aroma with a    Example IX          pleasant fruityness.    Fragrance formulation of                        A sweet, floral aroma    Example X           with excellent fruity                        floralcy undertones.    ______________________________________

EXAMPLE XIII

The following shampoo is prepared containing the following ingredients:

    ______________________________________    Ingredients            Parts by Weight    ______________________________________    Tridecyloxy polyethoxy ethanol                           17.3    of ten ethoxy groups    Polyoxyethylene (20) sorbitan                           7.5    monolaurate    Myristyl dimethylamine oxide                           25.0    (30% active)    C.sub.10 --C.sub.20 fatty acyl monoethanolamide                           2.5    (cocomonoethanolamide)    Polyacrylamide of molecular weight                           0.2    of about 1,500,000    Hydrogen peroxide (30% aqueous                           0.5    solution)    Perfume ingredient as indicated at                           1.0    Table V (below) giving rise to    the aroma profiles as indicated    in Table V (below)    Deionized water (3 micromhos/cm                           46.0    conductivity)    ______________________________________

A shampoo of the above composition is made in the following matter.First, the tridecyloxy polyethoxy ethanol is added to a clean mixingtank, with the agitator on, and the amine oxide, polyoxyethylenesorbitan monolaurate and cocomonoethanolamine are added sequentially,with continued agitation. The mix is then heated to 68° C., until thecocomonoethanolamide is melted and/or dissolved. The hydrogen peroxidesolution is then admixed with the mentioned nonionics and mixing iscontinued for about half an hour, in which the peroxide destroys anyfree amines or other harmful impurities that may be present. The mix isthen cooled to 38° C.

In a separate mixer the polyacrylamide is gradually added to the formulaweight of deionized water, with the mixer on. Addition is effectedcarefully and slowly (the polyacrylamide is sprinkled in) to avoid theproduction of "fish eyes" in the mix. After dissolving of thepolyacrylamide the solution thereof is added to the first mixing tankwith agitation and is blended with the nonionics, such mixings being atroom temperature. Subsequently the perfume as indicated in Table V(below) giving rise to the aroma profile as set forth in Table V (below)is admixed with the balance of the composition and mixing is continuedfor another half hour.

                  TABLE V    ______________________________________    Product           Aroma Profile    ______________________________________    Product produced according to                      A fruity, banana and    Example I, bulked fractions                      creamy aroma with    4-7 consisting of compounds                      camphoraceous and    having the structures:                      minty undertones.     ##STR215##    and     ##STR216##    Product produced according to                      A fruity, camphoraceous    Example II, bulked fractions                      and herbaceous aroma.    4-6 consisting of the compounds    having the structures:     ##STR217##    and     ##STR218##    Product produced according to                      A sweet, spicy, herbal    Example III, bulked fractions                      woody and eucalyptol-    7 and 8 consisting of the                      like aroma with a dis-    compounds having the structures:                      tinct calamnus undertone.     ##STR219##    and     ##STR220##    Product produced according to                      A sweet, fruity (banana)    Example IV, bulked fractions                      creamy and minty aroma    7-12 consisting of compounds                      with the minty nuances    having the structures:                      increasing in intensity                      on dryout.     ##STR221##    and     ##STR222##    Product produced according to                      A fruity, banana and    Example V, bulked fractions                      creamy aroma profile.    6-8 consisting of the compounds    having the structures:     ##STR223##    and     ##STR224##    Product produced according to                      A rum/butterscotch    Example VI, bulked fractions                      and balsamic aroma.    5-14 containing and consisting    of the compounds having the    structures:     ##STR225##    and     ##STR226##    Product produced according to                      A green, minty, borneol-    Example VII, bulked fractions                      like, spicy, somewhat    6-9 consisting of the compounds                      medicinal aroma reminis-    having the structures:                      cent of pepacuana bark                      extract with strong                      pepacuana bark-like under-                      tones     ##STR227##    and     ##STR228##    Fragrance formulation of                      A spicy, floral, herbal    Example VIII(A)   aroma with pleasant                      fruity tagette character-                      istics.    Fragrance formulation of                      A spicy, floral, herbal    Example VIII(B)   aroma with pleasant                      fruity tagette character-                      istics.    Fragrance formulation of                      A jasmine aroma with a    Example IX        pleasant fruityness.    Fragrance formulation of                      A sweet, floral aroma    Example X         with excellent fruity                      floralcy undertones.    ______________________________________

The product made is an excellent shampoo of satisfactory viscosity andaroma, foaming power, foam stability, low conductivity and goodshampooing effects. The viscosity is about 1,000 centipoises at 20° C.and the conductivity, using the Hach Conductivity Meter, is 750micromhos/cm. The foaming power is 250 ml and the foam stability is 22seconds, by the test method previously described. In comparison, acommercial shampoo based on triethanolamine lauryl sulphate detergenthas a conductivity of about 22,000 micromhos/cm, a viscosity of about1,500 centipoises, a foaming power of about 380 ml and a foam stabilityof 60 seconds.

In panel evaluations of the experimental shampoo compared to a differentcommercial product, in actual shampooing, the experimental formula wasadjudged significantly better in being less drying, producing a softerfeel for the wet hair, leaving the wet hair easier to comb, being lessprone to accumulate static charges (less flyaway) and having a foam ofbetter appearance and feel. Additionally, the experimental product wasjudged better in almost all hair effect properties, with the controlonly being about equal to it in curl retention. In properties other thanthose mentioned the experimental product was better in rinsability, thecontrol was better in foam build-up rate and the foams were about equalin volume and stability.

In the shampooing described herein and in subsequent Examples the humanhair is washed on the head by wetting the hair with warm tap water atabout 42° C., applying 15 grams of shampoo to the hair, lathering itinto the hair for a minute, rinsing with warm tap water for 30 seconds,re-lathering with 7 grams of shampoo for a minute and rinsing off for 30seconds, after which the hair is towel dried and dried further with anautomatic hair dryer.

EXAMPLE XIV FABRIC FRESHENER COMPOSITION

A fabric freshener composition is prepared as follows:

    ______________________________________    Ingredients        Parts by Weight    ______________________________________    Sodium bicarbonate 3    "Kyro" EOB (Trade Mark)*                       1    Perfume ingredient as set                       1    forth in Table VI below    giving rise to an aroma    as set forth in Table VI    below    Water              0.05    ______________________________________

The composition of this Example is prepared by simply mixing theingredients.

The above described composition is applied to a lightly soiled andwrinkled fabric as droplets (ca. 5.0 mm avg. size) using a trigger actonsprayer having a nozzle which is adjustable to provide compositiondroplets in the desire range. The composition is applied at a rate ofabout 1 gram of composition to about 10 grams of fabric.

The fabric is then placed in an automatic dryer and dried, with tumblingaction, at a temperature of 60° C.-80° C. for a period of 15 minutes.The fabric is rendered free of wrinkles and static, and has a freshappearance and pleasant odor profile as set forth in Table VI below.Suprisingly, the sodium bicarbonate is not visible on the refreshedfabric.

In the foregoing procedure, substantially the same results were obtainedwhen sodium carbonate is substituted for the sodium bicarbonate.

                  TABLE VI    ______________________________________    Product           Aroma Profile    ______________________________________    Product produced according to                      A fruity, banana and    Example I, bulked fractions                      creamy aroma with    4-7 consisting of compounds                      camphoraceous and    having the structures:                      minty undertones.     ##STR229##    and     ##STR230##    Product produced according to                      A fruity, camphoraceous    Example II, bulked fractions                      and herbaceous aroma.    4-6 consisting of the compounds    having the structures:     ##STR231##    and     ##STR232##    Product produced according to                      A sweet, spicy, herbal    Example III, bulked fractions                      woody and eucalyptol-    7 and 8 consisting of the                      like aroma with a dis-    compounds having the structures:                      tinct calamnus undertone.     ##STR233##    and     ##STR234##    Product produced according to                      A sweet, fruity (banana)    Example IV, bulked fractions                      creamy and minty aroma    7-12 consisting of compounds                      with the minty nuances    having the structures:                      increasing in intensity                      on dryout.     ##STR235##    and     ##STR236##    Product produced according to                      A fruity, banana and    Example V, bulked fractions                      creamy aroma profile.    6-8 consisting of the compounds    having the structures:     ##STR237##    and     ##STR238##    Product produced according to                      A rum/butterscotch    Example VI, bulked fractions                      and balsamic aroma.    5-14 containing and consisting    of the compounds having the    structures:     ##STR239##    and     ##STR240##    Product produced according to                      A green, minty, borneol-    Example VII, bulked fractions                      like, spicy, somewhat    6-9 consisting of the compounds                      medicinal aroma reminis-    having the structures:                      cent of pepacuana bark                      extract with strong                      pepacuana bark-like under-                      tones.     ##STR241##    and     ##STR242##    Fragrance formulation of                      A spicy, floral, herbal    Example VIII(A)   aroma with pleasant                      fruity tagette character-                      istics.    Fragrance formulation of                      A spicy, floral, herbal    Example VIII(B)   aroma with pleasant                      fruity tagette character-                      istics.    Fragrance formulation of                      A jasmine aroma with a    Example IX        pleasant fruityness.    Fragrance formulation of                      A sweet, floral aroma    Example X         with excellent fruity                      floralcy undertones.    ______________________________________     *A commercial nonionic surfactant comprising an average of eleven carbon     atoms, ethoxylated to an average of 9 ethyleneoxy groups per molecule.

EXAMPLE XV PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salts of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with aromas as indicated in Table VII below areprepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.40%, 0.50% and0.80% of the perfume ingredient as set forth in Table VII below. Thedetergents are prepared by adding a homogeneously mixing the appropriatequantity of perfume ingredient as set forth in Table VII below. Thedetergents all possess aromas as set forth in Table VII below with theintensity of each increasing with greater concentrations of the perfumeingredient as indicated in Table VII below.

                  TABLE VII    ______________________________________    Product            Aroma Profile    ______________________________________    Product produced according to                       A fruity, banana and    Example I, bulked fractions                       creamy aroma with    4-7 consisting of compounds                       camphoraceous and    having the structures:                       minty undertones.     ##STR243##    and     ##STR244##    Product produced according to                       A fruity, camphoraceous    Example II, bulked fractions                       and herbaceous aroma.    4-6 consisting of the compounds    having the structures:     ##STR245##    and     ##STR246##    Product produced according to                       A sweet, spicy, herbal    Example III, bulked fractions                       woody and eucalyptol-    7 and 8 consisting of the                       like aroma with a dis-    compounds having the structures:                       tinct calamnus undertone.     ##STR247##    and     ##STR248##    Product produced according to                       A sweet, fruity (banana)    Example IV, bulked fractions                       creamy and minty aroma    7-12 consisting of compounds                       with the minty nuances    having the structures:                       increasing in intensity                       on dryout.     ##STR249##    and     ##STR250##    Product produced according to                       A fruity, banana and    Example V, bulked fractions                       creamy aroma profile.    6-8 consisting of the compounds    having the structures:     ##STR251##    and     ##STR252##    Product produced according to                       A rum/butterscotch    Example VI, bulked fractions                       and balsamic aroma.    5-14 containing and consisting    of the compounds having the    structures:     ##STR253##    and     ##STR254##    Product produced according to                       A green, minty, borneol-    Example VII, bulked fractions                       like, spicy, somewhat    6-9 consisting of the compounds                       medicinal aroma reminis-    having the structures:                       cent of pepacuana bark                       extract with strong                       pepacuana bark-like under-                       tones.     ##STR255##    and     ##STR256##    Fragrance formulation of                       A spicy, floral, herbal    Example VIII(A)    aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A spicy, floral, herbal    Example VIII(B)    aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A jasmine aroma with a    Example IX         pleasant fruityness.    Fragrance formulation of                       A sweet, floral aroma    Example X          with excellent fruity                       floralcy undertones.    ______________________________________

EXAMPLE XVI PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The perfume ingredient as set forth in Table VIII below is incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 5.0%and 6.0% in 75%, 80%, 85%, 90% and 95% aqueous ethanol solutions.Distinct and definite aromas as set forth in Table VIII below areimparted to the colognes. The perfume ingredients as indicated in TableVIII below are also added to handkerchief perfumes at concentrations of15%, 20%, 25%, 30% and 35% (in 75%, 80%, 85%, 90% and 95% aqueousethanol) and aroma profiles as set forth in Table VIII are imparted tothe handkerchief perfume.

                  TABLE VIII    ______________________________________    Product            Aroma Profile    ______________________________________    Product produced according to                       A fruity, banana and    Example I, bulked fractions                       creamy aroma with    4-7 consisting of compounds                       camphoraceous and    having the structures:                       minty undertones.     ##STR257##    and     ##STR258##    Product produced according to                       A fruity, camphoraceous    Example II, bulked fractions                       and herbaceous aroma.    4-6 consisting of the compounds    having the structures:     ##STR259##    and     ##STR260##    Product produced according to                       A sweet, spicy, herbal    Example III, bulked fractions                       woody and eucalyptol-    7 and 8 consisting of the                       like aroma with a dis-    compounds having the structures:                       tinct calamnus undertone.     ##STR261##    and     ##STR262##    Product produced according to                       A sweet, fruity (banana)    Example IV, bulked fractions                       creamy and minty aroma    7-12 consisting of compounds                       with the minty nuances    having the structures:                       increasing in intensity                       on dryout.     ##STR263##    and     ##STR264##    Product produced according to                       A fruity, banana and    Example V, bulked fractions                       creamy aroma profile.    6-8 consisting of the compounds    having the structures:     ##STR265##    and     ##STR266##    Product produced according to                       A rum/butterscotch    Example VI, bulked fractions                       and balsamic aroma.    5-14 containing and consisting    of the compounds having the    structures:     ##STR267##    and     ##STR268##    Product produced according to                       A green, minty, borneol-    Example VII, bulked fractions                       like, spicy, somewhat    6-9 consisting of the compounds                       medicinal aroma reminis-    having the structures:                       cent of pepacuana bark                       extract with strong                       pepacuana bark-like under-                       tones.     ##STR269##    and     ##STR270##    Fragrance formulation of                       A spicy, floral, herbal    Example VIII(A)    aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A spicy, floral, herbal    Example VIII(B)    aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A jasmine aroma with a    Example IX         pleasant fruityness.    Fragrance formulation of                       A sweet, floral aroma    Example X          with excellent fruity                       floralcy undertones.    ______________________________________

EXAMPLE XVII BLUEBERRY FLAVOR FORMULATION

The following formulation is prepared:

    ______________________________________    Ingredients         Parts by Weight    ______________________________________    Heliotropin         3.0    Terpinenol-4 (10% in 95%    aqueous food grade ethanol)                        0.2    Benzaldehyde        1.5    Anisaldehyde        0.2    Phenyl acetaldehyde 0.4    Benzyl formate      0.5    Benzyl acetate      2.0    Cis-3-hexenyl benzoate (10%    in 95% aqueous food grade    ethanol)            0.5    Methyl hexanoate    2.0    Hexanal             1.0    Eucalyptol (1% in 95% aqueous    food grade ethanol) 0.5    Eugenol             0.2    Acetaldehyde        3.0    Ethyl acetate       21.0    Ethyl butyrate      26.0    Propylene glycol    38.0                        100.0    ______________________________________

The above formulation is split into 5 portions. To the first fourportions are added at the rate of 1%, the norbornane derivatives ofTable IX. To the fifth portion nothing is added. All five formulationswith and without said norbornyl derivatives are combined with water atthe rate of 100 ppm. The flavor of the first four portions eachincluding a norbornyl derivative prepared according to the preceedingexamples as indicated in Table IX below have fruity, blueberrycharacteristics with several other nuances as indicated in Table IXbelow and are all closely similar to the flavor of wild blueberries. Itis therefore preferred to use the formulations containing the norbornylderivatives as listed in Table IX below, to the basic blueberryformulation which does not contain any of said norbornyl derivatives.

                  TABLE IX    ______________________________________    Norbornyl Derivative                      Flavor Characteristics    ______________________________________    Composition produced according                      A fruity, blueberry aroma    to Example II consisting of                      and taste.    bulked fractions 4-6 contain-    ing the compounds having    the structures:     ##STR271##    and     ##STR272##    The composition of Example III                      A sweet, fruity, berry-    bulked fractions 7 and 8 con-                      like, spicy, black pepper-    taining the compounds having                      like, herbaceous and clove-    the structures:   like aroma and taste                      characteristic.     ##STR273##    and     ##STR274##    Composition of Example V                      A sweet, fruity, raspberry,    bulked fractions 6-8 con-                      vermouth-like and blueberry    taining the compounds hav-                      aroma profile with a fruity,    ing the structures:                      raspberry and blueberry                      flavor profile.     ##STR275##    and     ##STR276##    Composition produced                      A fruity, strawberry, blue-    according to Example VI                      berry, balsamic aroma profile    bulked fractions 5-14                      with blueberry, balsamic and    containing the compounds                      bitter profile at 2ppm.    having the structures:     ##STR277##    and     ##STR278##    ______________________________________

EXAMPLE XVIII USE OF NORBORNANE DERIVATIVES FOR RASPBERRY FLAVORS

The following basic raspberry formulation is prepared:

    ______________________________________    Ingredients         Parts By Weight    ______________________________________    Vanillin            2    Maltol              4    Parahydroxy benzyl acetone                        5    Dimethyl sulfide    1    Alpha-ionone (10% in propylene    glycol)             2    Ethyl butyrate      6    Ethyl acetate       16    Isobutyl acetate    14    Acetic acid         10    Acetaldehyde        10    Propylene glycol    930                        1000    ______________________________________

The above formulation is split into five parts. Two the first fourparts, at the rate of 0.3% are added the norbornyl derivative producedaccording to the preceeding examples, as set forth in Table X below. Noadditive is added to the fifth part. The five formulations are comparedin water at the rate of 50 ppm. The four flavors containing thenorbornyl derivatives have more ripe raspberry tastes and woody,raspberry kernel characters. They also have additional nuances as setforth in Table X below. Therefore the raspberry formulations containingthe four norbornyl derivatives as additives have more natural-like andmore characteristic raspberry flavors and are therefore preferred.

                  TABLE X    ______________________________________    Norbornyl Derivative                     Flavor Profile    ______________________________________    Product produced accord-                     A sweet, fruity, berry-like,    ing to Example III,                     spicy, black pepper-like,    bulked fractions 7 and 8                     herbaceous and clove-like    consisting of compounds                     aroma and taste.    having the structures:     ##STR279##    and     ##STR280##    Product produced according                     A sweet, fruity, red berry,    to Example IV, bulked                     raspberry-like and seedy    fractions 7-12 consisting                     aroma profile with a sweet,    of the compounds having                     fruity, red berry-like,    the structures:  raspberry-like, seedy and                     strawberry taste profile     ##STR281##    and     ##STR282##    Product produced according                     A sweet, fruity, raspberry,    to Example V, bulked                     vermouth-like and blueberry    fractions 6-8, consisting                     aroma profile with a fruity,    of the compounds having                     raspberry and blueberry    the structures:  flavor profile.     ##STR283##    and     ##STR284##    Product produced according                     A fruity, raspberry and seedy    to Example VII, bulked                     aroma profile with a fruity,    fractions 6-9, consisting                     raspberry, seedy and bitter    of the compounds having                     flavor profile    the structures:     ##STR285##    and     ##STR286##    ______________________________________

EXAMPLE XIX FRUITED TAPIOCA CREAM

The contents of Ann Page Tapioca pudding mix (ingredients: sugar, cornstarch, tapioca, sodium chloride, tapioca flavor and artificial color;Net weight 138 grams) is emptied into a sauce pan. Three cups of milkare added together with one beaten egg yolk previously blendedtherewith. The resulting mix is cooked over medium heat stirringconstantly while slowly adding at the rate of 0.2%, either one of theflavor materials of Example XVII (blueberry flavor) or one of the flavormaterials of Example XVIII (raspberry flavor) each of the materialscontaining one of the norbornyl derivatives of Table IX or of Table X asthe case may be. The resulting mixture after heating, is then cooled toroom temperature in the saucepan. One egg white is slowly added to theresulting mixture together with three tablespoons of sugar. Theresulting mixture is then blended and chilled yielding pleasantlytasting blueberry or raspberry tapioca cream deserts depending uponwhether the materials of Example XVII or Example XVIII are added.

EXAMPLE XX FLAVORED INSTANT PUDDING

A pudding mix (Royal Instant, Net weight 3.5 ozs. produced by StandardBrands Inc., New York, New York 10022) is intimately admixed with 2 cupsof cold fresh whole milk. To this mixture, at the rate of 0.3%, is addedone of the blueberry flavors of Example XVII containing the norbornylderivative as listed in Table IX or one of the raspberry flavors ofExample XVIII containing one of the norbornyl derivatives as listed inTable X. The resulting mixture is blended in a Waring blender for aperiod of three minutes. The resulting mixture is then cooled at 15° C.for a period of five minutes. The resulting puddings have excellentnatural blueberry or natural raspberry flavors as the case may be,depending on whether the blueberry flavors of Example XVII or whetherthe raspberry flavors of Example XVIII are used.

EXAMPLE XXI A. POWDER FLAVOR COMPOSITION

20 Grams of one of the flavor compositions of Example XVII (containingat least one of the norbornyl derivatives of Table IX) is emulsified ina solution containing 300 grams gum acacia and 700 grams water. Theemulsion is spray-dried with a Bowen Lab Model Drier utilizing 260c.f.m. of air with an inlet temperature of 500° F., an outlettemperature of 200° F., and a wheel of speed of 50,000 rpm.

B. SUSTAINED RELEASE FLAVOR

The following mixture is prepared:

    ______________________________________    Ingredients        Parts by Weight    ______________________________________    Liquid Blueberry Flavor,    composition of Ex. XVII                       20    Propylene glycol   9    Cab-O-Sil® M-5 (Brand of    Silica produced by the    Cabot Corp. of 125 High St.    Boston, Mass. 02110;    Physical Properties:    Surface area: 200 m.sup.2 /gm    Nominal particle size: 0.012    microns    Density: 2.3 lbs./cu. ft.                       5.00    ______________________________________

The Cab-O-Sil is dispersed in the liquid blueberry flavor compositions(containing the norbornyl derivatives) of Example XVII with vigorousstirring, thereby resulting in a viscous liquid. 71 Parts by weight ofthe powder flavor composition of Part A, supra, is then blended into thesaid viscous liquid, with stirring, at 25° C. for a period of 30 minutesresulting in a dry, free flowing sustained release flavor powder.

EXAMPLE XXII

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of the one of the liquid flavor compositionsof Example XVII (containing at least one of the norbornyl derivatives ofTable IX) is added to the solution which is then homogenized to form anemulsion having particle size typically in the range of 2-5 microns.This material is kept at 120° F. under which conditions the gelatin withnot jell.

Coascervation is induced by adding, slowly and uniformyl 40 parts byweight of a 20% aqueous solution of sodium sulphate. During coacervationthe gelatin molecules are deposited uniformly about each oil droplet asa nucleus.

Gelatin is effected by pouring the heated coascervate mixture into 1,000parts by weight of 7% aqueous solution of sodium sulphate at 65° F. Theresulting jelled coascervate may be filtered and washed with water attemperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde.

EXAMPLE XXIII

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XXI. 300 Parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum as a pleasant, long lastingblue-berry flavor.

EXAMPLE XXIV CHEWING GUM

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example XXII. 300 Parts of sucroseand 100 parts of corn syrup are then added. Mixing is effected in aribbon blender with jacketed side walls of the type manufactured by theBaker Perkins Co.

The resulting chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastingblueberry flavor.

EXAMPLE XXV TOOTHPASTE FORMULATION

The following separate groups of ingredients areprepared:______________________________________Parts by WeightIngredients______________________________________Group "A"30.200Glycerine15.325 Distilled Water.100 Sodium Benzoate.125 SaccharinSodium.400 Stannous FluorideGroup "B"12.500 Calcium Carbonate37.200Dicalsium Phosphate (Dihydrate)Group "C"2.000 Sodium N--LauroylSarcosinate (foaming agent)Group "D"1.200 Flavor Material of Ex.XVI100.00 Total______________________________________

PROCEDURE

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing, until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodiumn-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste when used in a normal toothbrushing procedureyields a pleasant blueberry flavor, of constant strong intensitythroughout said procedure (1.1.5 minutes).

EXAMPLE XXVI CHEWABLE VITAMIN TABLETS

The flavor material (containing norbornyl derivatives) of Table X ofExample XVIII is added to a chewable vitamin tablet formulation at therate of 10 gm/Kg which chewable vitamin tablet formulation is preparedas follows:

In a Hobart Mixer the following materials are blended tohomogeneity:______________________________________ Gms/1000Tablets______________________________________Vitamin C (ascorbic acid)asascorbic acid-sodium ascorbatemixture 1:1 70.00Vitamin B₁ (thiaminemononitrate331/3% (Hoffman La Roche) 4.0Vitamin B₂ (roboflavin) asRocoat®roboflavin 331/3% 5.0Vitamin B₆ (pyridoxine hydrochloride)asRocoat® pyridoxine hydrochloride331/3% 4.0Niacinamide as Rocoat®niacinamide331/3% 33.0Calcium pantothenate 11.5Vitamin B₁₂(cyanocobalamin) asMerck 0.1% in gelatin 3.5Vitamin E (dl-alphatocopherylacetate) as dry Vitamin E acetate331/3% Roche 6.6d-Biotin0.044Flavor of Example XVIII containingnorbornyl derivatives of Table X(as indicated above)Certified lake color 5.0Sweetener - sodium saccharin1.0Magnesium stearate lubricant 10.0Mannitol q.s. to make500.0______________________________________

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 G dry Vitamin A Acetate and 0.6 gVitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant long lasting,consistently strong raspberry flavor for a period of 12 minutes.

EXAMPLE XXVII CHEWING TOBACCO

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15%Pennsylvania leaf) the following casing is sprayed at a rate of30%:______________________________________Ingredients Parts byWeight______________________________________Corn Syrup 60Licorice10Glycerine 20Fig Juice 4.6Prune Juice 5Flavor Material of Ex.XVIIContaining Norbornyl Deriva-tives as listed in Table IX0.4______________________________________

The resultant product is redried to a moisture content of 20%. Onchewing, this tobacco has an excellent substantially consistent,long-lasting blueberry nuance in conjunction with the tobacco note.

EXAMPLE XXVIII TOBACCO FORMULATION

A tobacco mixture is produced by admixing the followingingredients:______________________________________Ingredient Parts byWeight______________________________________Bright 40.1Burley24.9Maryland 1.1Turkish 11.6Stem (flue-cured) 14.2Glycerine 2.8Water5.3______________________________________

Cigarettes are prepared from this tobacco. The following flavorformulation is prepared:______________________________________IngredientParts by Weight______________________________________Ethyl butyrate.05Ethyl valerate .05Maltol 2.00Cocoa extract 26.00Coffee extract10.00Ethyl alcohol 20.00Water41.90______________________________________

The above-stated tobacco flavor formulation is applied at the rate of0.1% to all of the cigarettes produced using the above tobaccoformulation. Half of the cigarettes are then treated with 500 to 1,500ppm of one of the following norbornyl derivatives of Table XI asfollows:

                  TABLE XI    ______________________________________    A.      Product produced according to Example II,            bulked fractions 4-6 consisting of the            compounds having the structures:             ##STR287##            and             ##STR288##    B.      Composition of matter produced according to            Example III bulked fractions 7 and 8 consisting            of the compounds having the structures:             ##STR289##            and             ##STR290##    ______________________________________

The control cigarettes not containing the norbornyl derivatives as setforth in Table XI and the experimental cigarettes which contain thenorbornyl derivatives as set forth in Table XI are evaluated by pairedcomparison and the results are as follows:

The experimental cigarettes, are found, on smoking, to have a sweeter,spicy, woody-oriental, clove-like taste with much more body and muchmore natural tobacco-like aroma prior to smoking and on smoking in themainstream and the sidestream. The experimental cigarettes containingthe product produced according to Example II in addition have coolingnuances. The experimental cigarettes produced containing the productproduced according to Example III also have cinnamon bark nuances priorto and on smoking in the mainstream and in the sidestream.

All cigarettes are evaluated for smoke flavor with a 20 mm celluloseacetate filter.

Accordingly, it is concluded that the norbornyl derivatives set forth inTable XI produced according to the processes of Examples II and IIIenhance the tobacco-like taste and aroma particularly the oriental-liketaste of the blended cigarette imparting to it sweet, spicy andwoody-oriental tobacco-like nuances and in addition clove-like nuances.

EXAMPLE XXIX

The following is a description of a preferred embodiment of theinvention as carried out using a process wherein minute capsules havinga diameter in the range of 50 up to 500 microns were added to a wet webof reconstituted tobacco (weight ratio of dry web to drycapsules=1:0.04. The capsules and binder materials (weight ratio of drycapsule to dry binder=1:0.1 when placed among the tobacco fibers, wetthem and entangle with them and clothe them, thus in effect securing andbinding the capsules against migration through the sheet, therebyforming a subsident stratum. The majority of binder and associatedcapsules are caught in the sheet. Substantially no capsules migratethrough the sheet. When the wet tobacco web is dried, the binder shrinksby loss of solvent, leaving the dried polymeric binder material, and thecapsules remain in place relatively with respect to sheet thickness. Thesheets containing the capsules are then shredded and used in producingsmoking articles such as cigarettes. Such cigarettes are formed using awrapper, containing a fill of tobacco extending from one end of thewrapper to the other, and intimately admixed with the tobacco, aplurality of microcapsules each comprising an aromatic volatilesynthetic clove oil flavorant. The capsules are homogeneously spaced incontiguous relationship with the tobacco such that as the burning frontof the tobacco advances the length of the tobacco article, a concomitantelevation of temperature initiates consecutive rupture of the capsules(1) releasing the volatile synthetic clove oil-containing material whichemanates with smoke from the smoking article into the smoker's mouth and(2) yielding a crackling sound audible to the human ear.

Tragacanth gum solution and starch solution were prepared in thefollowing manner:

PART A Concentrated Tragacanth Gum Solution (Binder)

4.5 Pounds of dry tragacanth gum powder were stirred into 50 gallons ofwater, using a suitable mixer. Five minutes after all the powder hadbeen added, the mixer was turned off. The tragacanth gum solution wasallowed to stir for 2 hours, and then the mixer was turned on for 5minutes. Sitting for 2 additional hours, enabled the tragacanth gum tohydrate. After five minutes, the mixer was turned off, and the 55 gallondrum was covered. Just prior to combining the tragacanth gum solutionand the capsular slurry, 50 gallons of tragacanth gum solution wasdiluted with water to 3 percent tragacanth gum on a solids basis.

PART B Starch Solution

The hydrolyzed starch solution was prepared by heating a slurry of thestarch at 190 degrees Fahrenheit for a minumum of 15 minutes to providea 1 percent by weight, starch-in-water solution.

Capsule slurries were prepared in the following manner:

PART C Preparation of Synthetic Clove Oil

A mixture is prepared containing the following ingredients:

    ______________________________________    Ingredient              Percentage    ______________________________________    α-Caryophyllene   2.0    β-Caryophyllene    2.0    γ-Caryophyllene   10.0    Furfural                0.1    Eugenol                 65.0    Eugenyl Acetate         5.0    Acetyl Eugenols         5.9    Norbornol Derivatives as follows:    A.     Product produced according to                                5.0           Example II, bulked fractions           4-6 consisting of the compounds           having the structures:            ##STR291##           and            ##STR292##    B.     Composition of matter produced                                5.0           according to Example III bulked           fractions 7 and 8 consisting of           the compounds having           the structures:            ##STR293##           and            ##STR294##    ______________________________________

PART D Preparation of Capsular Slurry-Encapsulation of Synthetic CloveOil

Ten grams of gum arabic were dissolved at room temperature in 220 gramsof deionized water. The mixture was agitated until the gum arabic wasfully dissolved. In a separate 240 milliliter Erlenmeyer flask, 10.0grams of modified gelatin was mixed with 220.0 grams of deionized water.The gelatin was allowed to tumefy at room temperature and also thenwarmed in a water bath in about 40° C. With stirring so that the gelatinwas dissolved.

The gelatin solution and the gum arabic solution were poured into abeaker equipped with a stirrer. A flocculence indicating theprecipitation of the gelatin was noted. The temperature of the mixturewas decreased to 35° C. The speed of the stirrer was adjusted so that itwas turning only enough to keep the phases mixed. The pH of the mixturewas 4.50.

Into the beaker containing the mixture of gum arabic and gelatin waspoured 118.0 grams of synthetic clove oil as prepared in Part C. Thespeed of the stirrer was then adjusted to mix the colloids and the oil.The oil separated into droplets. Two drops of octyl alcohol were addedto prevent foaming. The progress of the coacervation was monitored bymeans of microscopic examination.

The temperature of the mixture was lowered to room temperature, e.g.,24° C. At the higher temperature of 31° C., colloid deposition wasobserved on the oil droplets. At 24° C., little colloid could beobserved in aqueous portions of the mixture. Deposition had ceased.Stirring was continued for 30 minutes, whereupon the reaction mixturewas cooled on an ice bath to 4° C. The reaction mixture was maintainedat this temperature for 200 minutes. (When hardening was desired, 1.0milliliters of a 25 percent glutaraldehyde in water per gram of gelatinis added.)

The internal phase of the capsules thus formed was approximately 80-90percent of the total weight of the capsules.

The capsules thus produced had diameters in the range of from 50 up to500 microns. They were coated with the binder onto a tobacco sheetmaterial which was shredded and used as a fill in the manufacture of asmoking article.

PART E Variation of the Encapsulation of Synthetic Clove Oil

A variation of the encapsulation procedure set forth immediately suprais shown below.

The solution of gum arabic was warmed to 38° C., placed in a Waringblender and stirred. The clove oil prepared in Part C was addedgradually while the speed of the blender was being increased until thesize of the clove oil droplets was approximately 50-500 microns. Themixture thus formed was poured into a 1,000 milliliter beaker containinggelatin, also at 38° C., and was stirred thoroughly. The temperature wasthen allowed to drop to room temperature and then further decreased to atemperature of 4° C. to 10° C. by means of an ice bath.

It is evident that the tobacco film or filaments can be made fromvarious types and combinations of tobacco. For instance, the tobaccosheet material can be made from relatively expensive tobacco such asLatakia in which it is highly desirous to use all waste because of thehigh price thereof. So, also, it may be formed of Burley or one or morescrap or waste cigarette type tobaccos and incorporated in accordancewith a particular cigarette manufacture's formula as if it were naturalcigarette tobacco leaves. Any desired formula can thus be maintained inaccordance with the demands of a manufacturer's particular brand usingone or more types of natural shredded tobacco leaves and admixed desiredquantities of shredded capsule containing tobacco film material orfilaments, either as a blending or flavoring medium or both or forpurposes of bulking.

In the case of the manufacture of cigarettes, according to the presentinvention, tobacco films are shredded into strands or the film is formeddirectly into filaments substantially the width of the strands ofnatural shredded tobacco and of any desired length. In the case ofcigars, the capsule containing films are use in large pieces much aslong filler tobacco and forming long filler cigars. In all cases theshredded film or filaments or film used in cigarettes and cigars can behandled either manually or by machine in the same manner as naturalshredded tobacco leaves or whole leaves or portions thereof. The amountof shredded capsule-containing reconstituted tobacco or pieces of thismaterial employed in a particular blend in cigarettes or cigars,respectively, will vary according to types of tobacco used in the sheetmaterial and the requirements of a particular manufacture.

EXAMPLE XXX PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of detergent powder (a low phosphate contentdetergent composition which contains 12% by weight phosphate builder, 8%hardness mineral ion insensitive detergent, 0.9% by weight maleicanhydride-vinyl compound co-polymer and 2% alkylene oxide condensationproduct prepared according to Example IV at column XI, of U.S. Pat. No.4,000,080 issued on Dec. 28, 1976) is intimately admixed with 0.15 gramsof one of the perfume materials of Table XII below until a substantiallyhomogeneous composition is obtained. This composition has an aroma asset forth in Table XII below which is pleasant and long lasting:

                  TABLE XII    ______________________________________    Product            Aroma Profile    ______________________________________    Product produced according to                       A fruity, banana and    Example I, bulked fractions                       creamy aroma with    4-7 consisting of compounds                       camphoraceous and    having the structures:                       minty undertones.     ##STR295##    and     ##STR296##    Product produced according to                       A fruity, camphoraceous    Example II, bulked fractions                       and herbaceous aroma.    4-6 consisting of the compounds    having the structures:     ##STR297##    and     ##STR298##    Product produced according to                       A sweet, spicy, herbal    Example III, bulked fractions                       woody and eucalyptol-    7 and 8 consisting of the                       like aroma with a dis-    compounds having the structures:                       tinct calamnus undertone.     ##STR299##    and     ##STR300##    Product produced according to                       A sweet, fruity (banana)    Example IV, bulked fractions                       creamy and minty aroma    7-12 consisting of compounds                       with the minty nuances    having the structures:                       increasing in intensity                       on dryout.     ##STR301##    and     ##STR302##    Product produced according to                       A fruity, banana and    Example V, bulked fractions                       creamy aroma profile.    6-8 consisting of the compounds    having the structures:     ##STR303##    and     ##STR304##    Product produced according to                       A rum/butterscotch    Example VI, bulked fractions                       and balsamic aroma.    5-14 containing and consisting    of the compounds having the    structures:     ##STR305##    and     ##STR306##    Product produced according to                       A green, minty, borneol-    Example VII, bulked fractions                       like, spicy, somewhat    6-9 consisting of the compounds                       medicinal aroma reminis-    having the structures:                       cent of pepacuana bark                       extract with strong                       pepacuana bark-like under-                       tones.     ##STR307##    and     ##STR308##    Fragrance formulation of                       A spicy, floral, herbal    Example VIII(A)    aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A spicy, floral, herbal    Example VIII(B)    aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A jasmine aroma with a    Example IX         pleasant fruityness.    Fragrance formulation of                       A sweet, floral aroma    Example X          with excellent fruity                       floralcy undertones.    ______________________________________

EXAMPLE XXXI PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents with aromas as set forth in Table XIIIbelow are prepared containing 0.10%, 0.15%, and 0.20% of the perfumeingredients set forth in Table XIII below. They are prepared by addingand homogeneously mixing the appropriate quantity of perfume ingredientset forth in Table XIII below in a liquid detergent which is ahomogeneous single-phase heavy duty liquid detergent compositioncontaining:

a. 12.5% by weight based on the free acid form of an anionic detersivesurfactant;

b. 0.5% magnesium sulfate;

c. 12% by weight of an ethoxylated nonionic detersive surfactant;

d. 3% by weight of a water-soluble bis(styrylsulfonate)biphenylbrightener; and

e. the balance of the composition being water, prepared according toU.S. Pat. No. 3,998,750 issued on Dec. 21, 1976. The detergents allpossess aromas as described in Table XIII below:

                  TABLE XIII    ______________________________________    Product            Aroma Profile    ______________________________________    Product produced according to                       A fruity, banana and    Example I, bulked fractions                       creamy aroma with    4-7 consisting of compounds                       camphoraceous and    having the structures:                       minty undertones.     ##STR309##    and     ##STR310##    Product produced according to                       A fruity, camphoraceous    Example II, bulked fractions                       and herbaceous aroma.    4-6 consisting of the compounds    having the structures:     ##STR311##    and     ##STR312##    Product produced according to                       A sweet, spicy, herbal    Example III, bulked fractions                       woody and eucalyptol-    7 and 8 consisting of the                       like aroma with a dis-    compounds having the strucutures:                       tinct calamnus undertone.     ##STR313##    and     ##STR314##    Product produced according to                       A sweet, fruity (banana)    Example IV, bulked fractions                       creamy and minty aroma    7-12 consisting of compounds                       with the minty nuances    having the structures:                       increasing in intensity                       on dryout.     ##STR315##    and     ##STR316##    Product produced according to                       A fruity, banana and    Example V, bulked fractions                       creamy aroma profile.    6-8 consisting of the compounds    having the structures:     ##STR317##    and     ##STR318##    Product produced according to                       A rum/butterscotch    Example VI, bulked fractions                       and balsamic aroma.    5-14 contained and consisting    of the compounds having the    structures:     ##STR319##    and     ##STR320##    Product produced according to                       A green, minty, borneol-    Example VII, bulked fractions                       like, spicy, somewhat    6-9 consisting of the compounds                       medicinal aroma reminis-    having the structures:                       cent of pepacuana bark                       extract with strong                       pepacuana bark-like under-                       tones.     ##STR321##    and     ##STR322##    Fragrance formulation of                       A spicy, floral, herbal    Example VIII(A)    aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A spicy, floral, herbal    Example VIII(B)    aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A jasmine aroma with a    Example IX         pleasant fruityness.    Fragrance formulation of                       A sweet, floral aroma    Example X          with excellent fruity                       floralcy undertones.    ______________________________________

EXAMPLE XXXII PREPARATION OF MIXTURE OF ISOPROPYL ESTERS OF 5-METHYL AND6-METHYL-2-NORBORNANE CARBOXYLIC ACIDS (THERMAL NON-CATALYTICDIELS-ALDER REACTION) ##STR323##

Into a 500 cc high pressure stainless steel autoclave equipped withshaker are placed 140 grams of methylcyclopentadiene dimer, 200 grams ofisopropyl acrylate and 1 gram of Ionol®. The autoclave is closed andheated to 200° C. and maintained at 200° C. for a period of 10 hours. Atthe end of the 10 hour period, the autoclave is opened and the contentscooled to room temperature.

The reaction mass is then distilled on a fractional distillation columnyielding the following fractions:

    ______________________________________           Vapor    Liquid   Head          Weight    Fraction           Temp.    Temp.    Vac.    Reflux                                           of    Number °C.                    °C.                             mm Hg.  Ratio Fraction    ______________________________________    1      57/65    107/110  3.0/2.9 9:1   14.3    2      65       113      1.8     9:1   12    3      65       118      1.6     9:1   16    4      68       121      1.6     9:1   18    5      68       126      1.6     9:1   15.5    6      68       138      1.6     9:1   16.8    7      68       153      1.6     9:1   17.8    8      72       169      1.4     9:1   17.8    9      79       177      1.4     9:1   10.1    10     121      209      2.0     9:1   8    11     124      217      2.2     9:1   14.9    12     128      226      2.2     9:1   14.2    13     119      250      2.2     9:1   8.6    ______________________________________

FIG. 34 is the GLC profile of the reaction product prior to distillation(conditions: carbowax column programmed at 80°-220° C. at 8° C. perminute).

FIG. 35-A is the NMR spectrum for Peak 1 of the GLC profile of FIG. 34containing the compound having the structure: ##STR324##

FIG. 35-B is the NMR spectrum for Peak 2 of the GLC profile of FIG. 34containing the compound having the structure: ##STR325##

FIG. 36-A is the infra-red spectrum for Peak 1 of the GLC profile ofFIG. 34 containing the compound having the structure: ##STR326##

FIG. 36-B is the infra-red spectrum for Peak 2 of the GLC profile ofFIG. 34 containing the compound having the structure: ##STR327##

EXAMPLE XXXIII PREPARATION OF ETHYL ESTER OF 1-; 4-; 5-; and6-METHYL-2-NORBORNANE-CARBOXYLIC ACIDS (NON-CATALYTIC THERMALDIELS-ALDER REACTION) ##STR328##

Into a 1 liter autoclave is placed 400 grams of methylcyclopentadienedimer and 500 grams of ethyl acrylate. The autoclave is closed and thecontents are heated with stirring to a temperature of 200° C. andmaintained at that temperature for a period of 7 hours. The autoclavepressure is 25 psig. At the end of the 7 hour period, the autoclave isdepressurized and opened and the contents cooled to room temperature.

The contents of the autoclave are then distilled on a fractionaldistillation column yielding the followingfractions:______________________________________ Vapor Liquid HeadWeightFraction Temp. Temp. Vac. Reflux ofNumber °C. °C. mm. Hg. RatioFraction______________________________________1 53/60 84/80 18/30 4:1512 60 82 3.0 4:1 663 60 82 3.0 4:1 1104 62 83 3.0 4:1 835 67 87 3.0 4:11126 67 93 3.0 4:1 1077 62 105 3.0 4:1 1038 62 139 3.0 4:1 439 66 2253.0 4:1 47______________________________________

FIG. 37 is the GLC profile of the reaction product prior todistillation. Conditions: programmed at 80°-220° C. at 8° C. per minute:SE-30 column.

FIG. 38-A is the NMR spectrum for Fraction 1, Peak 1 of the distillationproduct of the reaction product of Example XXXIII containing thecompounds having the structures: ##STR329##

FIG. 38-B is the NMR spectrum for Fraction 8, Peak 2 of the distillationproduct of the reaction product of Example XXXIII containing thecompounds having the structures: ##STR330##

FIG. 39-A is the infra-red spectrum for Fraction 1, Peak 1 of thedistillation product of the reaction product of Example XXXIIIcontaining the compounds having the structures: ##STR331##

FIG. 39-B is the infra-red spectrum for Fraction 8, Peak 2 of thedistillation product of the reaction product of Example XXXIIIcontaining the compounds having the structures: ##STR332##

EXAMPLE XXXIV PREPARATION OF 1-; 4-; 5-; and 6-METHYL NORBORNANECARBOXYLIC ACID ETHEL ESTERS ##STR333##

Into a high pressure bottle equipped with Parr shaker is placed 200grams of the methyl cyclopentadiene-ethyl acrylate reaction productproduced according to Example XXXIII; 50 ml isopropyl alcohol and 5grams of Raney Nickel catalyst. The contents are purged with hydrogenand the bottle is then pressurized to 50 psig. While maintaining thehydrogen pressure at between 20 and 50 psig over a period of 13 hours,the reaction mass is shaken using the Parr shaker. At the end of the 13hour period the pressure bottle is opened and the reaction mass isdistilled on a 12 inch Goodloe column yielding the followingfractions:______________________________________ Vapor Liquid HeadWeightFraction Temp. Temp. Vac. Reflux ofNumber °C. °C. mm. Hg. RatioFraction______________________________________1 49/44 78/79 2.0/0.89:1/9:1 14.82 45 80 .35 4:1 16.83 45 80 .35 4:1 23.44 46 80 .35 4:124.35 46 80 .35 4:1 28.06 46 87 .35 4:1 22.37 48 88 .35 4:1 22.68 54 88.35 4:1 16.59 51 112 .35 4:1 13.610 49 230 .35 4:18.6______________________________________

FIG. 40-A is the NMR spectrum for Fraction 2, Peak 1 of the distillationproduct of the reaction product of Example XXXIV containing thecompounds having the structures: ##STR334##

FIG. 40-B is the NMR spectrum for Fraction 10, Peak 2 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR335##

FIG. 41-A is the infra-red spectrum for Fraction 2, Peak 1 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR336##

FIG. 41-B is the infra-red spectrum for Fraction 10, Peak 2 of thedistillation product of the reaction product of Example XXXIV containingthe compounds having the structures: ##STR337##

EXAMPLE XXXV PREPARATION OF 3,5- AND 3,6-DIMETHYL-2-NORBORNENECARBOXYLIC ACID ETHYL ESTERS ##STR338##

Into a 500 cc autoclave equipped for high pressure reactions is placed175 grams of methyl cyclopentadiene dimer; 250 grams of ethyl crotonateand 1 gram of Ionol®. The autoclave is closed and with stirring heatedto 200° C. and maintained at 200° C. under pressure for a period of 10hours. The contents of the autoclave are then cooled to room temperatureand the autoclave is opened. The autoclave is then emptied of itscontents and the contents are then distilled in an 18" silver columnwith Goodloe packing yielding the followingfractions:______________________________________ Vapor Liquid HeadWeightFraction Temp. Temp. Vac. Reflux ofNumber °C. °C. mm. Hg. RatioFraction______________________________________1 37/39 100/110 1.0/.8 9:1192 52 97 .8 9:1 223 52 97 .8 9:1 184 50 90 .8 9:1 195 50 90 .8 9:1 19650 91 .7 9:1 207 50 91 .7 9:1 208 50 91 .7 9:1 209 50 93 .7 9:1 2410 50101 .7 9:1 2211 50 119 .7 9:1 2412 50 124 .7 9:1 2213 50 143 .7 9:1 231464 163 .7 9:1 815 96 230 .7 9:1 1316 109 250 .7 9:110______________________________________

FIG. 42 is the GLC profile of the reaction product prior todistillation.

FIG. 43-A is the NMR spectrum for Peak 1 of the GLC profile of FIG. 42of the reaction product of Example XXXV containing the compound havingthe structure: ##STR339##

FIG. 43-B is the NMR spectrum for Peak 2 of the GLC profile of FIG. 42for the reaction product of Example XXXV containing the compound havingthe structure: ##STR340##

FIG. 44-A is the infra-red spectrum for Peak 1 of the GLC profile ofFIG. 42 of the reaction product of Example XXXV containing the compoundhaving the structure: ##STR341##

FIG. 44-B is the infra-red spectrum for Peak 2 of the GLC profile ofFIG. 42 of the reaction product of Example XXXV containing the compoundhaving the structure: ##STR342##

EXAMPLE XXXVI PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of detergent powder (a low phosphate contentdetergent composition which contains 12% by weight phosphate builder, 8%hardness mineral ion insensitive detergent, 0.9% by weight maleicanhydride-vinyl compound copolymer and 2% alkylene oxide condensationproduct prepared according to Example IV at column XI, of U.S. Pat. No.4,000,080 issued on Dec. 8, 1976) is intimately admixed with 0.15 gramsof one of the perfume materials of Table XIV below until a substantiallyhomogeneous composition is obtained. This composition has an aroma asset forth in Table XIV below which is pleasant and long lasting:

                  TABLE XIV    ______________________________________    Product            Aroma Profile    ______________________________________    Isopropyl ester of 5- and                       A green, fruity aroma.    6-methyl-5-norbornane-2-    carboxylic acid (thermal    non-catalytic Diels-alder    reaction) prepared according    to Example XXXII    Ethyl esters of 1-; 4-; 5-;                       A sweet, fruity, minty    and 6-methyl-5-norbornane-                       aroma.    2-carboxylic acid (thermal    non-catalytic Diels-alder    reaction) prepared according    to Example XXXIII    Ethyl ester of 1-; 4-; 5-;                       A fruity, banana and    and 6-methyl-norbornane-2-                       creamy aroma profile.    carboxylic acid (thermal    non-catalytic Diels-alder    reaction) prepared according    to Example XXXIV    Ethyl esters of 3,5- and                       An intense, fruity,    3,6-dimethyl-5-norbornane-                       strawberry-like, raspberry-    2-carboxylic acid (thermal                       like, reseda body-like    non-catalytic Diels-alder                       aroma but does not have    reaction) prepared according                       tagett nuances.    to Example XXXV    ______________________________________

EXAMPLE XXXVII PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents with aromas as set forth in Table XVbelow are prepared containing 0.10%, 0.15%, and 0.20% of the perfumeingredients set forth in Table XV below. They are prepared by adding andhomogeneously mixing the appropriate quantity of perfume ingredient setforth in Table XV below in a liquid detergent which is a homogeneoussingle-phase heavy duty liquid detergent composition containing:

a. 12.5% by weight based on the free acid form of an anionic detersivesurfactant;

b. 0.5% magnesium sulfate;

c. 12% by weight of an ethoxylated nonionic detersive surfactant;

d. 3% by weight of a water-soluble bis(styrylsulfonate)biphenylbrightener; and

e. the balance of the composition being water, prepared according toU.S. Pat. No. 3,998,750 issued on Dec. 21, 1976. The detergents allpossess aromas as described in Table XV below:

                  TABLE XV    ______________________________________    Product            Aroma Profile    ______________________________________    Product produced according to                       A fruity, banana and    Example I, bulked fractions                       creamy aroma with    4-7 consisting of compounds                       camphoraceous and    having the structures:                       minty undertones.     ##STR343##    and     ##STR344##    Product produced according to                       A fruity, camphoraceous    Example II, bulked fractions                       and herbaceous aroma.    4-6 consisting of the compounds    having the structures:     ##STR345##    and     ##STR346##    Product produced according to                       A sweet, spicy, herbal    Example III, bulked fractions                       woody and eucalyptol-    7 and 8 consisting of the                       like aroma with a dis-    compounds having the strucutres:                       tinct calamnus undertone.     ##STR347##    and     ##STR348##    Product produced according to                       A sweet, fruity (banana)    Example IV, bulked fractions                       creamy and minty aroma    7-12 consisting of compounds                       with the minty nuances    having the structures:                       increasing in intensity                       on dryout.     ##STR349##    and     ##STR350##    Product produced according to                       A fruity, banana and    Example V, bulked fractions                       creamy aroma profile.    6-8 consisting of the compounds    having the structures:     ##STR351##    and     ##STR352##    Product produced according to                       A rum/butterscotch    Example VI, bulked fractions                       and balsamic aroma.    5 -14 containing and consisting    of the compounds having the    structures:     ##STR353##    and     ##STR354##    Product produced according to                       A green, minty, borneol-    Example VII, bulked fractions                       like, spicy, somewhat    6-9 consisting of the compounds                       medicinal aroma reminis-    having the structures:                       cent of pepacuana bark                       extract with strong                       pepacuana bark-like under-                       tones.     ##STR355##    and     ##STR356##    Fragrance formulation of                       A spicy, floral, herbal    Example VIII (A)   aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A spicy, floral, herbal    Example VIII (B)   aroma with pleasant                       fruity tagette character-                       istics.    Fragrance formulation of                       A jasmine aroma with a    Example IX         pleasant fruityness.    Fragrance formulation of                       A sweet, floral aroma    Example X          with excellent fruity                       floralcy undertones.    Isopropyl ester of 5- and 6-                       A green, fruity aroma.    methyl-5-norbornane-2-    carboxylic acid (thermal    non-catalytic Diels-alder    reaction) prepared according    to Example XXXII    Ethyl esters of 1-; 4-; 5-;                       A sweet, fruity, minty    and 6-methyl-5-norbornane-                       aroma.    2-carboxylic acid (thermal    non-catalytic Diels-alder    reaction) prepared according    to Example XXXIII    Ethyl esters of 1-; 4-; 5-;                       A fruity, banana and    and 6-methyl-norbornane-                       creamy aroma profile.    carboxylic acid (thermal    non-catalytic Diels-alder    reaction) prepared according    to Example XXXIV    Ethyl esters of 3,5- and                       An intense, fruity,    3,6-dimethyl-5-norbornane-                       strawberry-like, rasp-    2-carboxylic acid (thermal                       berry-like, reseda body-    non-catalytic Diels-alder                       like aroma but does not    reaction) prepared according                       have tagett nuances.    to Example XXXV    ______________________________________

What is claimed is:
 1. A fabric softener composition comprising a fabricsoftener base and intimately admixed therewith an aroma augmenting orenhancing quantity of at least one compound defined according to thestructure: ##STR357## wherein the dashed line represents a carbon-carbonsingle bond or a carbon-carbon double bond; R₁ ', R₂ ', R₃ ', R₄ ', R₆', and R₇ ' are each selected from the group consisting of hydrogen andmethyl and R₅ ' is C₁ -C₄ alkyl with the provisos that:
 1. one of R₁ ',R₂ ', R₆ ' and R₇ ' is methyl and the other of R₁ ', R₂ ', R₆ ' and R₇ 'represents hydrogen;2. R₃ ' and R₄ ' are not both methyl;
 3. when thedashed line is a carbon-carbon double bond, R₁ ', R₃ ' and R₄ ' are notall hydrogen when R₂ ' is methyl.
 2. A process for augmenting orenhancing the aroma of a dryer-added fabric softener article or an aromaimparted by a dryer-added fabric softener article comprising the step ofadding to at least one component of a dryer-added fabric softenerarticle and aroma augmenting or enhancing quantity of at least onecompound defined according to the generic structure: ##STR358## whereinthe dashed line represents a carbon-carbon single bond or acarbon-carbon double bond; R₁ ', R₂ ', R₃ ', R₄ ', R₆ ', and R₇ ' areeach selected from the group consisting of hydrogen and methyl and R₅ 'is C₁ -C₄ alkyl with the provisos that:
 1. one of R₁ ', R₂ ', R₆ ' andR₇ ' is methyl and the other of R₁ ', R₂ ', R₆ ' and R₇ ' representshydrogen;2. R₃ ' and R₄ ' are not both methyl;
 3. when the dashed lineis a carbon-carbon double bond, R₁ ', R₃ ' and R₄ ' are not all hydrogenwhen R₂ ' is methyl.